KR20220016111A - Mono-bidentate ligand, bis-bidentate ligand and tetra-bidentate ligand Guanidine Group 4 transition metal olefin copolymerization catalyst - Google Patents

Abstract

.A process for polymerizing polyolefins comprises the step of contacting ethylene and optionally one or more (C ₃ -C ₁₂ )α-olefins in the presence of a catalyst system, wherein the catalyst system is a metal-ligand having a structure according to formula (I). Complexes include:

.

Description

Mono-bidentate ligand, bis-bidentate ligand and tetra-bidentate ligand Guanidine Group 4 transition metal olefin copolymerization catalyst

Cross-reference to related applications

This application claims priority to U.S. Provisional Patent Application No. 62/855,306, filed on May 31, 2019, the entire contents of which are incorporated herein by reference.

technical field

Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and methods, and more specifically to mono-bidentate ligands, bis-bidentate ligands and tetradentate ligand Group 4 transition metal catalysts. It relates to an olefin polymerization catalyst system comprising: and an olefin polymerization method comprising the catalyst system.

Olefin-based polymers such as polyethylene, ethylene-based polymers, polypropylene and propylene-based polymers are prepared via a variety of catalyst systems. The choice of such a catalyst system used in the polymerization process of the olefinic polymer is an important factor contributing to the characteristics and properties of the olefinic polymer.

Ethylene-based polymers are prepared for a wide variety of articles. Polyethylene polymerization methods can be modified in many respects to produce a wide variety of final polyethylene resins with different physical properties, thereby making the various resins suitable for use in a variety of applications. The ethylene monomer and optionally one or more comonomers are present in a liquid diluent (eg solvent) such as an alkane or isoalkane, eg isobutene. Hydrogen may also be added to the reactor. Catalyst systems for producing ethylene systems typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems and/or molecular (metallocene or non-metallocene) catalyst systems. can do. The reactants and catalyst system in diluent are cycled at an elevated polymerization temperature around the reactor to produce the ethylenic homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture comprising the polyethylene product dissolved in the diluent is removed from the reactor along with unreacted ethylene and one or more optional comonomers. The reaction mixture may be treated to remove polyethylene product from the diluent and unreacted reactants when removed from the reactor, the diluent and unreacted reactants are typically recycled back to the reactor. Alternatively, the reaction mixture may be sent to a second reactor connected in series to the first reactor, where a second polyethylene fraction may be formed.

Despite the large number of homogeneous solution olefin polymerization catalyst systems currently available, the range of incorporation of high molecular weight (Mw) polymers and/or comonomers with narrow polydispersity (PDI) (i.e. 0 to 20 mol %) 1-hexene or 1-octene, etc.) with a high molecular weight (Mw) ethylene/comonomer copolymer and/or chain transfer agent (CSA) and chain transfer proceeds to produce an olefin block copolymer (OBC) There is a need for high-temperature polymerization catalysts with improved molecular properties that facilitate the production of capable high molecular weight (Mw) polymers.

Embodiments of the present disclosure include polymerization methods. These polymerization methods produce ethylene-based polymers. The polymerization process comprises contacting ethylene and optionally one or more (C ₃ -C ₁₂ )α-olefins in the presence of a catalyst system, wherein the catalyst system is a metal-ligand complex having a structure according to formula (I). includes:

In formula (I), M is titanium, zirconium or hafnium. each X is unsaturated (C ₂ -C ₂₀ )hydrocarbon, unsaturated (C ₂ -C ₅₀ )heterohydrocarbon, (C ₁ -C ₅₀ )hydrocarbyl, (C ₁ -C ₅₀ )heterohydrocarbyl, (C ₆ - C ₅₀ )aryl, (C ₆ -C ₅₀ )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C ₄ -C ₁₂ )diene, halogen, -OR ^X , -N(R ^X ) ₂ or a monodentate or bidentate ligand independently selected from -NCOR ^X , wherein each R ^x is (C ₁ -C ₃₀ )hydrocarbyl or -H. (X) The subscript _n of n is 1, 2 or 3. the subscript m is 1 or 2; m+n equals 3 or 4 (m + n = 3 or 4).

In formula (I), each R ¹ is R ^1a or R ^1b ; each R ⁴ is R ^4a or R ^4b ; R ^1a , R ^1b , R ^4a and R ^4b are -H, (C ₂ -C ₄₀ )hydrocarbyl, (C ₁ -C ₄₀ )heterohydrocarbyl, -Si(R ^C ) ₃ , -Ge(R ^C ) ₃ , -P(R ^P ) ₂ , -N(R ^N ) ₂ , -OR ^C , -SR ^C , -NO ₂ , -CN, -CF ₃ , R ^C S(O)-, R ^C S(O ) ₂ -, (R ^C ) ₂ C=N-, R ^C C(O)O-, R ^C OC(O)-, R ^C C(O)N(R)-, (R ^C ) ₂ NC( O)- or halogen.

In formula (I), each A is independently —NR ² R ³ ; each R ² is R ^2a or R ^2b ; each R ³ is R ^3a or R ^3b ; R ^2a , R ^2b , R ^3a and R ^3b are independently —H or (C ₁ -C ₄₀ )hydrocarbyl; provided that when (1) m is 2 and (2) R ^2a , R ^2b , R ^3a and R ^3b are all methyl, then at least one of R ^1a , R ^1b , R ^4a and R ^4b is not 2-propyl and ; when m is 1, each X is equal; Any of R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ may optionally be joined to form a ring.

1 is a general synthesis scheme that can be used to synthesize the ligand.
2 is a synthesis scheme for the synthesis of Ligand 1;
3 to 5 are structural formulas of ligands of the present disclosure.

A specific embodiment of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments presented in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

Common abbreviations are listed below:

R, Z, M, X and n : as defined above; Me : methyl; Et : ethyl; Et : phenyl; Bn : benzyl; i -Pr : iso -propyl; t - Bu : tert -butyl; t -Oct : tert -octyl (2,4,4-trimethylpentan-2-yl); Tf : trifluoromethane sulfonate; THF : tetrahydrofuran; Et ₂ O : diethyl ether; CH ₂ Cl ₂ : dichloromethane; CV : column volume (used in column chromatography); EtOAc : ethyl acetate; C ₆ D ₆ : deuterated benzene or benzene- d 6; CDCl ₃ : deuterated chloroform; Na ₂ SO ₄ : sodium sulfate; MgSO ₄ : magnesium sulfate; HCl : hydrogen chloride; n -BuLi : butyllithium; t - BuLi : tert -butyllithium; Cu ₂ O : copper (I) oxide; N,N'- DMEDA: N,N' -dimethylethylenediamine; K ₃ PO ₄ : potassium triphosphate; Pd(AmPhos)Cl ₂ : bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); Pd(dppf)Cl ₂ : [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride; AgNO ₃ : silver nitrate; K ₂ CO ₃ : potassium carbonate; Cs ₂ CO ₃ : cesium carbonate; i - PrOBPin : 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane; BrCl ₂ CCCl ₂ Br : 1,2-dibromotetrachloroethane; HfCl ₄ : hafnium chloride (IV); HfBn ₄ : tetrabenzyl hafnium (IV); ZrCl ₄ : zirconium chloride (IV); ZrBn ₄ : tetrabenzyl zirconium (IV); ZrBn ₂ Cl ₂ (OEt ₂ ) : zirconium(IV) dibenzyl dichloride mono-diethyletherate; HfBn ₂ Cl ₂ (OEt ₂ ) : hafnium(IV) dibenzyl dichloride mono-diethyletherate; TiBn ₄ : tetrabenzyl titanium (IV); Zr(CH ₂ SiMe ₃ ) ₄ : tetrakis-trimethylsilylmethyl zirconium (IV); Hf(CH ₂ SiMe ₃ ) ₄ : tetrakis-trimethylmethyl hafnium(IV); N ₂ : nitrogen gas; PhMe : toluene; PPR : Parallel pressure reactor; MAO : methylaluminoxane; MMAO : modified methylaluminoxane; GC : gas chromatography; LC : liquid chromatography; NMR : nuclear magnetic resonance; MS : mass spectrometer; mmol : millimoles; mL : milliliter; M : mole; min or mins : minutes; h or hrs : hours; d : work; R _f : residual fraction; TLC : thin layer chromatography; rpm : revolutions per minute.

The term "independently selected", followed by a plurality of selections, means that each R group appearing before the term, eg, R ¹ , R ² , R ³ , R ⁴ and R ⁵ , refers to any other group that also appears before the term. Used herein to refer to something that can be the same or different, regardless of identity.

The term “procatalyst” refers to a compound that has catalytic activity when combined with an activator. The term “activator” refers to a compound that chemically reacts with a procatalyst in such a way that it catalytically converts the procatalyst to an active catalyst. As used herein, the terms “cocatalyst” and “activator” are interchangeable terms.

When used to describe a particular carbon atom-containing chemical group, parenthesis expressions having the form "(C _x -C _y )" indicate that the unsubstituted form of the chemical group is from x carbon atoms to y carbons, including x and y. It means to have atoms. For example, (C ₁ -C ₅₀ )alkyl is an alkyl group having from 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted with one or more substituents, such as R ^S . R ^S substituted versions of chemical groups defined using the "(C _x -C _y )" parentheses may contain more than y carbon atoms depending on the identity of any R ^S group. For example, “(C ₁ -C ₅₀ )alkyl substituted with exactly one group R ^S , wherein R ^S is phenyl(—C ₆ H ₅ )” may contain from 7 to 56 carbon atoms. Thus, generally, when a chemical group defined using the "(C _x -C _y )" parentheses is substituted with one or more carbon atom-containing substituents R ^S , then the minimum and maximum total number of carbon atoms in that chemical group is x and y is determined by adding to all the combined sum of the number of carbon atoms from all carbon atom-containing substituents R ^S .

The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of the unsubstituted compound or functional group is replaced with a substituent (eg, R ^S ). The term “oversubstituted” means that all hydrogen atoms (H) bonded to carbon atoms or heteroatoms of the unsubstituted compound or functional group are replaced with a substituent (eg, R ^S ). The term "polysubstituted" means that at least two but less than all hydrogen atoms bonded to carbon atoms or heteroatoms of the unsubstituted compound or functional group are replaced by a substituent. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly specified.

The term “(C ₁ -C ₅₀ )hydrocarbyl” means a hydrocarbon radical having 1 to 50 carbon atoms, and the term “(C ₁ -C ₅₀ )hydrocarbylene” refers to a hydrocarbon radical having 1 to 50 carbon atoms divalent radical, wherein each hydrocarbon radical and each hydrocarbon divalent radical are aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having at least 3 carbons, monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic, and unsubstituted or substituted with one or more R ^S .

In the present disclosure, (C ₁ -C ₅₀ )hydrocarbyl is unsubstituted or substituted (C ₁ -C ₅₀ )alkyl, (C ₃ -C ₅₀ )cycloalkyl, (C ₃ -C ₂₀ )cycloalkyl-( C ₁ -C ₂₀ )alkylene, (C ₆ -C ₄₀ )aryl or (C ₆ -C ₂₀ )aryl-(C ₁ -C ₂₀ )alkylene (eg benzyl(CH ₂ -C ₆ H ₅ ) )) can be

The terms “(C ₁ -C ₅₀ )alkyl” and “(C ₁ -C ₁₈ )alkyl” refer to a saturated straight or branched hydrocarbon radical of 1 to 50 carbon atoms and a saturated straight chain of 1 to 18 carbon atoms, respectively. or a branched hydrocarbon radical, which is unsubstituted or substituted with one or more R ^S . Examples of unsubstituted (C ₁ -C ₅₀ )alkyl include unsubstituted (C ₁ -C ₂₀ )alkyl; unsubstituted (C ₁ -C ₁₀ )alkyl; unsubstituted (C ₁ -C ₅ )alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Examples of substituted (C ₁ -C ₄₀ )alkyl are substituted (C ₁ -C ₂₀ )alkyl, substituted (C ₁ -C ₁₀ )alkyl, trifluoromethyl and [C ₄₅ ]alkyl. The term “[C ₄₅ ]alkyl” means that there are up to 45 carbon atoms in the radical, including substituents, eg (C ₂₇ ) individually substituted with one R ^S which is (C ₁ -C ₅ )alkyl. -C ₄₀ )alkyl. Each (C ₁ -C ₅ )alkyl may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl or 1,1-dimethylethyl.

The term "(C ₆ -C ₅₀ )aryl" means a monocyclic, bicyclic or tricyclic aromatic hydrocarbon radical of 6 to 40 carbon atoms, unsubstituted or substituted (with one or more R ^S ), at least 6 of which The to 14 carbon atoms are aromatic ring carbon atoms. monocyclic aromatic hydrocarbon radicals contain one aromatic ring; A bicyclic aromatic hydrocarbon radical has two rings; A tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the radical rings is aromatic. The other ring or rings of the aromatic radical may independently be fused or unfused, and may be aromatic or non-aromatic. Examples of unsubstituted (C ₆ -C ₅₀ )aryl include: unsubstituted (C ₆ -C ₂₀ )aryl, unsubstituted (C ₆ -C ₁₈ )aryl; 2-(C ₁ -C ₅ )alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl and phenanthrene. Examples of substituted (C ₆ -C ₄₀ )aryl include: substituted (C ₁ -C ₂₀ )aryl; substituted (C ₆ -C ₁₈ )aryl; 2,4-bis([C ₂₀ ]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-on-1-yl.

The term “(C ₃ -C ₅₀ )cycloalkyl” means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms, unsubstituted or substituted with one or more R ^S . Other cycloalkyl groups (eg, (C _x -C _y )cycloalkyl) are defined in a similar manner as having x to y carbon atoms, unsubstituted or substituted with one or more R ^S . Examples of unsubstituted (C ₃ -C ₄₀ )cycloalkyl include unsubstituted (C ₃ -C ₂₀ )cycloalkyl, unsubstituted (C ₃ -C ₁₀ )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of substituted (C ₃ -C ₄₀ )cycloalkyl are substituted (C ₃ -C ₂₀ )cycloalkyl, substituted (C ₃ -C ₁₀ )cycloalkyl, cyclopentanon-2-yl and 1-fluoro It is cyclohexyl.

Examples of (C ₁ -C ₅₀ )hydrocarbylene include unsubstituted or substituted (C ₆ -C ₅₀ )arylene, (C ₃ -C ₅₀ )cycloalkylene and (C ₁ -C ₅₀ )alkylene (eg for example, (C ₁ -C ₂₀ )alkylene). Divalent radicals may be on the same carbon atom (eg -CH ₂ -) or on adjacent carbon atoms (ie 1,2-divalent radicals), or may have 1, 2 or more than 2 intervening carbons. They are separated by atoms (eg, 1,3-1-valent radicals, 1,4-divalent radicals, etc.). Some divalent radicals include 1,2-, 1,3-, 1,4- or α,ω-divalent radicals, and other divalent radicals include 1,2-divalent radicals. An α,ω divalent radical is a divalent radical having the largest carbon skeleton spacing between the radical carbons. Some examples of (C ₂ -C ₂₀ )alkylene α,ω divalent radicals are ethane-1,2-diyl (ie —CH ₂ CH ₂ —), propane-1,3-diyl (ie —CH ₂ CH ₂ CH ₂ —), 2-methylpropane-1,3-diyl (ie, —CH ₂ CH(CH ₃ )CH ₂ —). Some examples of (C ₆ -C ₅₀ )arylene α,ω-divalent radicals include phenyl-1,4-diyl, naphthalene-2,6-diyl or naphthalene-3,7-diyl.

The term “(C ₁ -C ₅₀ )alkylene” means a saturated straight or branched chain divalent radical of 1 to 50 carbon atoms (ie, no radical is present on a ring atom), which is unsubstituted or one It is substituted with the above R ^S . Examples of unsubstituted (C ₁ -C ₅₀ )alkylene include unsubstituted -CH ₂ CH ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₇ -, -(CH ₂ ) ₈ -, -CH ₂ C*HCH ₃ and -(CH ₂ ) ₄ C*(H)(CH ₃ ) unsubstituted ( C ₁ -C ₂₀ )alkylene, wherein “C*” represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C ₁ -C ₅₀ )alkylene include substituted (C ₁ -C ₂₀ )alkylene, -CF ₂ -, -C(O)- and -(CH ₂ ) ₁₄ C(CH ₃ ) ₂ (CH ₂ ) ₅ -(ie, normal-1,20-eicosylene substituted with 6,6-dimethyl). Examples _{of substituted (C 1 -C 50} ⁾ _{alkylene also} include _1,2 -bis( methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane and 2,3-bis(methylene)bicyclo [2.2.2] Contains octane.

The term “(C ₃ -C ₅₀ )cycloalkylene” means a cyclic divalent radical of 3 to 50 carbon atoms (ie the radical is on a ring atom), unsubstituted or substituted with one or more R ^S . do.

The term “heteroatom” refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom are O, S, S(O), S(O) _{2 ,} Si( ^RC ) _{2 ,} P(R ^P ), N(R ^N ), —N = ^C (RC) ₂ , -Ge(RC ) ₂ -, or -Si( ^RC )-, wherein each R ^C and each R ^P is unsubstituted ( ^C ₁ -C ₁₈ )hydro carbyl or —H, and each R ^N is unsubstituted (C ₁ -C ₁₈ )hydrocarbyl. The term “heterohydrocarbon” refers to a molecule or molecular backbone in which one or more carbon atoms of a hydrocarbon have been replaced with a heteroatom. The term "(C ₁ -C ₅₀ )heterohydrocarbyl" means a heterohydrocarbyl radical of 1 to 50 carbon atoms, and the term "(C ₁ -C ₅₀ )heterohydrocarbylene" refers to a heterohydrocarbyl radical of 1 to 50 carbon atoms. Heterohydrocarbon divalent radical. The heterohydrocarbon of (C ₁ -C ₅₀ )heterohydrocarbyl or (C ₁ -C ₅₀ )heterohydrocarbylene has one or more heteroatoms. The radical of a heterohydrocarbyl may be on a carbon atom or a heteroatom. The two radicals of heterohydrocarbylene may be on a single carbon atom or on a single heteroatom. Furthermore, one of the two radicals of a divalent radical may be on a carbon atom and the other radical may be on a different carbon atom; One of the two radicals may be on a carbon atom and the other on a heteroatom; One of the two radicals may be on a heteroatom and the other radical may be on a different heteroatom. each (C ₁ -C ₅₀ )heterohydrocarbyl and (C ₁ -C ₅₀ )heterohydrocarbylene is unsubstituted or substituted (with one or more R ^S ) aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or non-cyclic.

(C ₁ -C ₅₀ )Heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of (C ₁ -C ₅₀ )heterohydrocarbyl include (C ₁ -C ₅₀ )heteroalkyl, (C ₁ -C ₅₀ )hydrocarbyl-O-, (C ₁ -C ₅₀ )hydrocarbyl-S -, (C ₁ -C ₅₀ )hydrocarbyl-S(O)-, (C ₁ -C ₅₀ )hydrocarbyl-S(O) ₂ -, (C ₁ -C ₅₀ )hydrocarbyl-Si(R ^C ) ₂ -, (C ₁ -C ₅₀ )hydrocarbyl-N(R ^N )-, (C ₁ -C ₅₀ )hydrocarbyl-P(R ^P )-, (C ₂ -C ₅₀ )heterocycloalkyl, (C ₂ -C ₁₉ )heterocycloalkyl-(C ₁ -C ₂₀ )alkylene, (C ₃ -C ₂₀ )cycloalkyl-(C ₁ -C ₁₉ )heteroalkylene, (C ₂ -C ₁₉ )heterocycloalkyl -(C ₁ -C ₂₀ )heteroalkylene, (C ₁ -C ₅₀ )heteroaryl, (C ₁ -C ₁₉ )heteroaryl-(C ₁ -C ₂₀ )alkylene, (C ₆ -C ₂₀ )aryl -(C ₁ -C ₁₉ )heteroalkylene or (C ₁ -C ₁₉ )heteroaryl-(C ₁ -C ₂₀ )heteroalkylene.

The term “(C ₄ -C ₅₀ )heteroaryl” refers to monocyclic, bicyclic or tricyclic heteroaromatic of 4 to 50 total carbon atoms and 1 to 10 heteroatoms, unsubstituted or substituted (with one or more R ^S ). hydrocarbon radicals. monocyclic heteroaromatic hydrocarbon radicals contain one heteroaromatic ring; A bicyclic heteroaromatic hydrocarbon radical has two rings; A tricyclic heteroaromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the radical rings is heteroaromatic. The other ring or rings of the heteroaromatic radical may independently be fused or unfused, and may be aromatic or non-aromatic. Other heteroaryl groups (eg, generally (C _x -C _y )heteroaryl, eg (C ₄ -C ₁₂ )heteroaryl) are in a similar manner x to y carbon atoms (eg, 4 to 12 carbon atoms) and is unsubstituted or substituted with one or more than one R ^S . A monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring. 5-membered rings have 5 - h carbon atoms, where h is the number of heteroatoms and can be 1, 2 or 3; Each heteroatom can be O, S, N or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. A 6-membered ring has 6 - h carbon atoms, where h is the number of heteroatoms, and may be 1 or 2, and the heteroatoms may be N or P. Examples of 6 membered ring heteroaromatic hydrocarbon radicals include pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical may be a fused 5,6- or 6,6-ring system. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radicals include indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radicals include quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical is a fused 5,6,5-; 5,6,6-; 6,5,6-; or a 6,6,6-ring system. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

The term “(C ₁ -C ₅₀ )heteroalkyl” means a saturated straight or branched chain radical containing from 1 to 50 carbon atoms or fewer carbon atoms and at least one heteroatom. The term “(C ₁ -C ₅₀ )heteroalkylene” means a saturated straight or branched chain divalent radical containing from 1 to 50 carbon atoms and one or more than one heteroatom. The heteroatom of heteroalkyl or heteroalkylene is Si( ^RC ) ₃ , Ge( ^RC ) ₃ , Si( ^RC ) ₂ , Ge( ^RC ) _{2 , P(RP ) 2 ,} ^P ( ^RP ) , N(R ^N ) ₂ , N(R ^N ), N, O, OR ^C , S, ^SRC , S(O) and S(O) ₂ , each heteroalkyl and heteroalkylene The group is unsubstituted or substituted with one or more R ^S .

Examples of unsubstituted (C ₂ -C ₄₀ )heterocycloalkyl include unsubstituted (C ₂ -C ₂₀ )heterocycloalkyl, unsubstituted (C ₂ -C ₁₀ )heterocycloalkyl, aziridin-1-yl, oxetane -2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxane- 2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl and 2-aza-cyclodecyl.

The term "halogen atom" or "halogen" means a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br) or an iodine atom (I). The term “halide” refers to the anionic form of a halogen atom: fluoride (F ⁻ ), chloride (Cl ⁻ ), bromide (Br ⁻ ) or iodide (I ⁻ ).

The term "saturated" means free of carbon-carbon double bonds, carbon-carbon triple bonds and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus and carbon-silicon double bonds. When the saturated chemical group is substituted with one or more substituents R ^S , one or more double and/or triple bonds may optionally be present or absent in the substituents R ^S . The term "unsaturated" is meant to contain one or more carbon-carbon double bonds or carbon-carbon triple bonds or (in heteroatom-containing groups) one or more carbon-nitrogen, carbon-phosphorus or carbon-silicon double bonds, but if It does not include double bonds which, if present, may be present in the substituent R ^S or in the (hetero)aromatic ring.

Embodiments of the present disclosure include polymerization methods. These polymerization methods produce ethylene-based polymers. The polymerization process comprises contacting ethylene and optionally one or more (C ₃ -C ₁₂ )α-olefins in the presence of a catalyst system, wherein the catalyst system is a metal-ligand complex having a structure according to formula (I). includes:

In formula (I), M is titanium, zirconium or hafnium. each X is unsaturated (C ₂ -C ₂₀ )hydrocarbon, unsaturated (C ₂ -C ₅₀ )heterohydrocarbon, (C ₁ -C ₅₀ )hydrocarbyl, (C ₁ -C ₅₀ )heterohydrocarbyl, (C ₆ - C ₅₀ )aryl, (C ₆ -C ₅₀ )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C ₄ -C ₁₂ )diene, halogen, -OR ^X , -N(R ^X ) ₂ or a monodentate or bidentate ligand independently selected from -NCOR ^X , wherein each R ^x is (C ₁ -C ₃₀ )hydrocarbyl or -H. (X) The subscript _n of n is 1, 2 or 3. the subscript m is 1 or 2; m+n equals 3 or 4 (m + n = 3 or 4).

in formula (I), each R ¹ is R ^1a or R ^1b ; each R ⁴ is R ^4a or R ^4b ; R ^1a , R ^1b , R ^4a and R ^4b are hydrogen (-H), (C ₂ -C ₄₀ )hydrocarbyl, (C ₆ -C ₄₀ )aryl, (C ₁ -C ₄₀ )heterohydrocarbyl, (C ₅ -C ₄₀ )heteroaryl, -Si(RC ) ₃ , ^-Ge (RC ) ₃ , -P( ^{RP ) 2 , -N(R N ) 2 , -OR C} _, ^-SR _C ^{, -NO} ₂ , -CN, -CF ₃ , R ^C S(O)-, R ^C S(O) ₂ -, (R ^C ) ₂ C=N-, R ^C C(O)O-, R ^C OC(O) )-, R ^C C(O)N(R)-, (R ^C ) ₂ NC(O)- or halogen.

In formula (I), each A is independently —NR ² R ³ ; each R ² is R ^2a or R ^2b ; each R ³ is R ^3a or R ^3b ; R ^2a , R ^2b , R ^3a and R ^3b are independently —H or (C ₁ -C ₄₀ )hydrocarbyl; provided that when (1) m is 2 and (2) R ^2a , R ^2b , R ^3a and R ^3b are all methyl, then at least one of R ^1a , R ^1b , R ^4a and R ^4b is not 2-propyl and ; when m is 1, each X is equal; Any of R ¹ and R ² or R ² and R ³ or R ³ and R ⁴ may optionally be joined to form a ring.

In some embodiments of Formula (I), when m is 2 and n is 2, the metal-ligand complex has a structure according to Formula (II):

In formula (II), R ^1a , R ^1b , R ^4a , R ^4b ; M and X are as defined in formula (I). A ¹ and A ² are independently A as defined in formula (I).

In one or more embodiments, each R ¹ , R ^1a or R ^1b and each R ⁴ , R ^4a or R ^4b of Formulas (I) and (II) is independently (C ₁ -C ₄₀ )alkyl, (C ₁ -C ₄₀ )heteroalkyl, (C ₆ -C ₄₀ )aryl or (C ₅ -C ₄₀ )heteroaryl.

In one or more embodiments, each R ¹ , R ^1a or R ^1b and each R ⁴ , R ^4a or R ^4b of Formulas (I) and (II) is independently benzyl, cyclohexyl, 2,6-dimethylphenyl , tert -butyl or ethyl.

In one or more embodiments, in formula (III) m is 2, n is 2 and R ^4a and R ^4b are covalently linked, whereby said metal-ligand complex comprises two covalently linked groups R ^4a and a divalent radical Q consisting of R ^4b . The metal-ligand complex has a structure according to formula (III):

In formula (III), Q is (C ₂ -C ₁₂ )alkylene, (C ₂ -C ₁₂ )heteroalkylene, (C ₆ -C ₅₀ )arylene, (C ₄ -C ₅₀ )heteroarylene, (-CH ₂ Si( ^RC ) ₂ CH ₂ -), (-CH ₂ CH ₂ Si( ^RC ) ₂ CH ₂ CH ₂ -), (-CH ₂ Ge( ^RC ) ₂ CH ₂ -) or ( —CH ₂ CH ₂ Ge(R ^C ) ₂ CH ₂ CH ₂ —); R ^1a , R ^1b , M and X are as defined in formula (I), and A ¹ and A ² are as defined in formula (II).

In one or more embodiments, Q in Formula (III) is selected from -(CH ₂ ) _x -, wherein x is 2-5. In some embodiments, Q is -(CH ₂ ) ₄ -.

In some embodiments, R ^1a and R ^1b of Formula (III) are 2-propyl or 2,6-dimethylphenyl.

In various embodiments, each A of formulas (I), (II) and (III) is carbazolyl, imidizolyl, indolyl, pyrrolyl, or pyrazolyl. In some embodiments, each of A, A ¹ and A ² is a ring structure having one of the structures:

.

.

In formulas (I), (II) and (III), each of A, A ¹ and A ² is independently —NR ² R ³ ; each R ² is R ^2a or R ^2b ; each R ³ is R ^3a or R ^3b . In one or more embodiments, R ^2a , R ^2b , R ^3a and R ^3b in Formulas (I), (II) and (III) are (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )heteroalkyl, (C ₁ -C ₂₀ )aryl or (C ₁ -C ₂₀ )heteroaryl. In some embodiments, R ^2a , R ^2b , R ^3a and R ^3b are methyl, ethyl, 1-propyl, 2-propyl, n-butyl, tert -butyl, 2-methylpropyl( iso -butyl), n-butyl , n-hexyl, cyclohexyl, n -octyl or tert -octyl.

In various embodiments, R ^1a , R ^1b , R ^4a and R ^4b in Formulas (I), (II), and (III) are independently selected from cyclohexyl, benzyl, 2-propyl, or 2,6-dimethylphenyl .

In one or more embodiments, when R ¹ and R ⁴ are 2-propyl, then R ² and R ³ are not methyl. In one or more embodiments, when R ¹ and R ⁴ are 2-propyl, then R ² and R ³ are not —N(CH ₃ ) ₂ . In one embodiment of formula (II), R ^1a is not covalently bonded to R ^2b or R ^3b to form a ring.

In the metal-ligand complexes according to formulas (I), (II) and (III), each X is bonded to M via a covalent bond, a dative bond or an ionic bond. In some embodiments, each X is the same. The metal-ligand complex may have up to six metal-ligand bonds and may be entirely neutral or may have a positive charge associated with the metal center. In some embodiments, the catalyst system comprises a metal-ligand complex according to formula (I), wherein M is zirconium or hafnium; each X is (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )heteroalkyl, (C ₆ -C ₂₀ )aryl, (C ₄ -C ₂₀ )heteroaryl, (C ₄ -C ₁₂ )diene or halogen.

In some embodiments, X is a monodentate ligand, and the monodentate ligand may be a monoanionic ligand. A monovalent anionic ligand has a net formal oxidation state of -1. Each monoanionic ligand is independently hydride, (C ₁ -C ₄₀ )hydrocarbyl carbocation, (C ₁ -C ₄₀ )heterohydrocarbyl carbocation, halide, nitrate, carbonate, phosphate, sulfate, HC ( O)O ^- , HC(O)N(H) ^- , (C ₁ -C ₄₀ )hydrocarbylC(O)O ^- , (C ₁ -C ₄₀ )hydrocarbylC(O)N((C ₁ - C ₂₀ )hydrocarbyl) ^- , (C ₁ -C ₄₀ )hydrocarbylC(O)N(H) ^- , R ^K R ^L B ^- , R ^K R ^L N ^- , R ^K O ^- , R ^K S ^- , R ^K R ^L P ^- or R ^M R ^K R ^L Si ^- , wherein each R ^K , R ^L and R ^M is independently hydrogen, (C ₁ -C ₄₀ )hydrocarbyl or (C ₁ - C ₄₀ )heterohydrocarbyl, or R ^K and R ^L are taken together to form (C ₂ -C ₄₀ )hydrocarbylene or (C ₁ -C ₂₀ )heterohydrocarbylene, and R ^M is as defined above same.

In other embodiments, at least one monodentate ligand X may be a neutral ligand independently of any other ligand X. In certain embodiments, the neutral ligand is a neutral Lewis base group, e.g., R ^Q NR ^K R ^L , R ^K OR ^L , R ^K SR ^L or R ^Q PR ^K R ^L , wherein each R ^Q is independently hydrogen, [(C ₁ -C ₁₀ )hydrocarbyl] ₃ Si(C ₁ -C ₁₀ )hydrocarbyl, (C ₁ -C ₄₀ )hydrocarbyl, [(C ₁ -C ₁₀ )hydrocarbyl] ₃ Si or ( C ₁ -C ₄₀ )heterohydrocarbyl, and each R ^K and R ^L is independently as defined above.

In addition, each X independently of any other ligand X is halogen, unsaturated (C ₁ -C ₂₀ )hydrocarbyl, unsaturated (C ₁ -C ₂₀ )hydrocarbylC(O)O- or R ^K R ^L N- monodentate ligand, wherein each R ^K and R ^L is independently an unsaturated (C ₁ -C ₂₀ )hydrocarbyl. In some embodiments, each monodentate ligand X is a chlorine atom, (C ₁ -C ₁₀ )hydrocarbyl (eg, (C ₁ -C ₆ )alkyl or benzyl), unsaturated (C ₁ -C ₁₀ )hydrocarbyl C(O)O- or R ^K R ^L N-, wherein each of R ^K and R ^L is independently unsubstituted (C ₁ -C ₁₀ )hydrocarbyl. In one or more embodiments of formulas (I), (II) and (III), X is benzyl, chloro, —CH ₂ SiMe ₃ or phenyl.

In a further embodiment, each X is methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chloro. In some embodiments, each X is the same. In other embodiments, at least two Xs are different from each other. In embodiments wherein at least two Xs are different from at least one X, X is methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chloro. In a further embodiment, the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

In some embodiments, any or all of the chemical groups (eg, X, R ¹ to R ⁴ ) of the metal-ligand complex of Formula (I) may be unsubstituted. In other embodiments, none of the chemical groups X, R ¹ to R ⁴ of the metal-ligand complex of Formula (I) can be substituted with one or more than one R ^S , or any of the chemical groups X, R ¹ to R ⁴ . Any or all may be substituted with one or more than one R ^S . When two or more than two R ^S are bonded to the same chemical group of a metal-ligand complex of formula (I), the individual R ^S of said chemical group are at the same carbon atom or heteroatom, or at different carbon atoms or heteroatoms. can be combined. In some embodiments, none of the chemical groups X, R ¹ -R ⁴ may be oversubstituted with RS, or any or all of the chemical groups X, R ¹ -R ⁴ may be ^{oversubstituted} with R ^S . In a chemical group oversubstituted with R ^S , individual R ^S may all be the same, or may be independently selected.

In an exemplary embodiment, the present catalyst system comprises a metal-ligand complex according to formula (I) having the structure of any of the procatalysts 1 to 74 described below synthesized from the corresponding ligands 1 to 17 as shown in FIGS. 3-5 . may include:

chain shuttling agents and/or chain shuttling agents

In one or more embodiments, the polymerization method of the present disclosure comprises contacting ethylene and/or one or more (C ₃ -C ₁₂ )α-olefins in a reactor in the presence of a catalyst system and a chain transfer agent or chain shuttling agent. . In this embodiment, the polymerization process comprises three components: (A) a procatalyst comprising a metal-ligand complex having the structure of formula (I) and optionally a cocatalyst; (B) an olefin polymerization catalyst having a different comonomer selectivity than that of the procatalyst (A); and (C) a chain transfer agent or chain shuttling agent.

By being added to the catalyst system, chain transfer agents and chain shuttling agents are compounds capable of transferring a polymer chain between two catalyst molecules in a single polymerization reactor. The catalyst molecules may have the same structure or different structures. When the catalyst molecules have different structures, they may have different monomer selectivities. Whether the compound acts as a chain transfer agent or chain shuttling agent depends on the type of polymerization reactor although the three components (A) to (C) described above may be chemically identical in either type of polymerization reactor. For example, in a batch reactor with a single-catalyst system or a dual-catalyst system, the compound acts as a chain transfer agent. In a continuous reactor with a dual-catalyst system, the compound acts as a chain shuttling agent. In general, compounds that act as chain shuttling agents in batch reactors can also act as chain shuttling agents in continuous reactors; Conversely, molecules that act as chain shuttling agents can also act as chain shuttling agents. Therefore, in embodiments of the polymerization process in the present disclosure, it is to be understood that the disclosure of a compound as a “chain transfer agent” further corresponds to the disclosure as a “chain shuttling agent” of the same compound. Thus, the terms "chain transfer agent" and "chain shuttling agent" are interchangeable with respect to chemical compounds, but may be distinguished when the process is specified to occur within a particular type of polymerization reactor.

)로부터 수 평균 사슬 길이(

)를 얼마나 감소시키는 지를 기재한다. 방정식 2는 사슬 이동 또는 사슬 왕복 상수, Ca를 사슬 이동 및 전파 속도 상수의 비율로서 정의한다. 대부분의 사슬 전파가 공단량체 혼입이 아니라 에틸렌 삽입을 통해서 발생한다고 가정함으로써, 방정식 3은 중합의 예상되는 Mn을 설명한다. Mn₀는 사슬 왕복제가 없는 경우 촉매의 고유 분자량이고, Mn은 사슬 왕복제가 존재하는 경우 관찰되는 분자량이다(Mn = 사슬 왕복제가 없는 경우 Mn₀).The chain transfer capacity of the catalyst is initially assessed by changing the level of the chain transfer agent or chain shuttling agent (CSA), thereby conducting a campaign observing the reduction in molecular weight and narrowing of the PDI expected for the shuttling catalyst. Molecular weights of polymers produced by catalysts that have the potential to have good chain shuttling will be more sensitive to the addition of CSA than those produced by catalysts exhibiting lowered round trips or slower chain transfer kinetics. Mayo's equation (Equation 1) shows that the chain transfer agent is an intrinsic number-average chain length (

) from the number average chain length (

) and how much it is reduced. Equation 2 defines the chain transfer or chain reciprocation constant, Ca , as the ratio of the chain transfer and propagation rate constants. By assuming that most of the chain propagation occurs through ethylene insertion and not comonomer incorporation, Equation 3 accounts for the expected Mn of the polymerization. Mn ₀ is the intrinsic molecular weight of the catalyst in the absence of chain shuttling agent, and Mn is the molecular weight observed in the presence of chain shuttling agent (Mn = Mn ₀ in the absence of chain shuttling agent).

Typically, the chain transfer agent is a metal that is Al, B or Ga in a formal oxidation state of +3; or metals that are Zn or Mg in a formal oxidation state of +2. Chain transfer agents suitable for the methods of the present disclosure are described in US Patent Application Publication No. US 2007/0167315, which is incorporated herein by reference in its entirety.

In one or more embodiments of the present polymerization process, the chain transfer agent, if present, is diethylzinc, di( iso -butyl)zinc, di( n -hexyl)zinc, di( n- octyl)zinc, triethylaluminum, trioctyl Aluminum, triethylgallium, iso -butylaluminum, bis(dimethyl(t-butyl)siloxane), iso -butylaluminum bis(di(trimethylsilyl)amide), n -octylaluminum di(pyridine-2-methoxide), Bis(n-octadecyl), iso -butylaluminum, iso -butylaluminum bis(di( n -pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide), n-octyl Aluminum di(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-di Benzo-1-azacycloheptanamide), n -octylaluminum bis(2,3,6,7-dibenzo-1-azacycloheptanamide), n-octylaluminum bis(dimethyl( t -butyl)siloxide) , ethylzinc (2,6-diphenylphenoxide), ethylzinc (t-butoxide), dimethylmagnesium, dibutylmagnesium and n -butyl- sec -butylmagnesium.

cocatalyst component

Catalyst systems comprising metal-ligand complexes of formula (I) may be catalytically activated by any technique known in the art for activating metal-based catalysts of olefin polymerization reactions. For example, a procatalyst according to a metal-ligand complex of formula (I) can be catalytically activated by contacting the complex with an activating cocatalyst or by combining the complex with an activating cocatalyst. Metal-ligand complexes according to formula (I) also include both neutral procatalyst forms and catalytic forms which can be positively charged due to loss of monovalent anionic ligands such as benzyl or phenyl. Activating cocatalysts suitable for use herein include alkyl aluminum; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acid; and non-polymerizable, non-coordinating ion-forming compounds, including the use of such compounds under oxidizing conditions. A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activating cocatalysts and techniques are also contemplated. The term “alkyl aluminum” means monoalkyl aluminum dihydride or monoalkylaluminum dihalide, dialkyl aluminum hydride or dialkyl aluminum halide or trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane and isobutylalumoxane.

Lewis acid activated cocatalysts include Group 13 metal compounds containing (C ₁ -C ₂₀ )hydrocarbyl substituents as described herein. In some embodiments, the Group 13 metal compound is a tri((C ₁ -C ₂₀ )hydrocarbyl)-substituted-aluminum or tri((C ₁ -C ₂₀ )hydrocarbyl)-boron compound. In another embodiment, the Group 13 metal compound is tri(hydrocarbyl)-substituted-aluminum, tri((C ₁ -C ₂₀ )hydrocarbyl)-boron compound, tri((C ₁ -C ₁₀ )alkyl)aluminum, tri((C ₆ -C ₁₈ )aryl)boron compounds and halogenated (including perhalogenated) derivatives thereof. In a further embodiment, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C ₁ -C ₂₀ )hydrocarbyl borate (eg, trityl tetrafluoroborate) or tri((C ₁ -C ₂₀ )hydrocarbyl)ammonium tetra(( C ₁ -C ₂₀ )hydrocarbyl)borane (eg, bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane) As used herein, the term “ammonium” means ((C ₁ - C ₂₀ )hydrocarbyl) ₄ N ⁺ , ((C ₁ -C ₂₀ )hydrocarbyl) ₃ N(H) ⁺ , ((C ₁ -C ₂₀ )hydrocarbyl) ₂ N(H) ₂ ⁺ , (C ₁ ) -C ₂₀ )hydrocarbylN(H) ₃ ⁺ or N(H) ₄ ⁺ means a nitrogen cation, wherein each (C ₁ -C ₂₀ )hydrocarbyl is the same or different when two or more are present. can do.

Combinations of neutral Lewis acid activated cocatalysts include combinations of tri((C ₁ -C ₄ )alkyl)aluminum with halogenated tri((C ₆ -C ₁₈ )aryl)boron compounds, particularly tris(pentafluorophenyl)borane. including mixtures that Another embodiment is the combination of such a neutral Lewis acid mixture with a polymeric or oligomeric alumoxane and a polymeric or oligomeric alumoxane with a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane. (Metal-ligand complex): (tris(pentafluoro-phenyl)borane):(alumoxane)[eg (Group 4 metal-ligand complex):(tris(pentafluoro-phenyl)borane):( alumoxane)] in a ratio of 1:1:1 to 1:10:30, and in another embodiment 1:1:1.5 to 1:5:10.

Catalyst systems comprising a metal-ligand complex of formula (I) may be activated by association with one or more cocatalysts, such as cation forming cocatalysts, strong Lewis acids, or combinations thereof to form an active catalyst composition. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, non-coordinating ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, and combinations thereof. .

In some embodiments, more than one of the aforementioned activating cocatalysts may be used in combination with one another. Specific examples of cocatalyst combinations are mixtures of tri((C ₁ -C ₄ )hydrocarbyl)aluminum, tri((C ₁ -C ₄ )hydrocarbyl)borane or ammonium borate with oligomeric or polymeric aluminoxane compounds. The ratio of the total moles of the at least one metal-ligand complex of formula (I) to the total moles of the at least one activating cocatalyst is from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments at least 1:1000; and 10:1 or less, and in some other embodiments 1:1 or less. When alumoxane is used alone as the activating cocatalyst, the number of moles of alumoxane used is preferably at least 100 times the number of moles of the metal-ligand complex of formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used versus the one or more metal-ligand complexes of Formula (I) The total number of moles is 0.5:1 to 10:1, 1:1 to 6:1 or 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of formula (I).

polyolefin

The catalyst systems described in the preceding paragraph are used for the polymerization of olefins, mainly ethylene and propylene. In some embodiments, only a single type of olefin or α-olefin is present in the polymerization scheme to produce a homopolymer. However, additional α-olefins may be incorporated in the polymerization process. The additional α-olefin comonomers typically have up to 20 carbon atoms. For example, the α-olefin comonomer may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methyl-1-pentene. Not limited. For example, the one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene; or alternatively, 1-hexene and 1-octene.

The ethylene-based polymers, such as homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more comonomers, such as α-olefins, will comprise at least 50% by weight of monomer units derived from ethylene. can All individual numbers and subranges encompassed by “at least 50% by weight” are disclosed herein as separate embodiments; For example, ethylene-based polymers, homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more comonomers, such as α-olefins, comprise at least 60% by weight of monomer units derived from ethylene; at least 70% by weight of monomer units derived from ethylene; at least 80% by weight of monomer units derived from ethylene; or 50 to 100% by weight of monomer units derived from ethylene; or 80 to 100% by weight of units derived from ethylene.

In some embodiments, the ethylene-based polymer may comprise at least 90 mol % of units derived from ethylene. All individual values and subranges from at least 90 mol % are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may comprise at least 93 mol % of units derived from ethylene; at least 96 mol % of units; at least 97 mol % of units derived from ethylene; or alternatively, from 90 to 100 mol % of units derived from ethylene; 90 to 99.5 mol % of units derived from ethylene; or 97 to 99.5 mol % of units derived from ethylene.

In some embodiments of the ethylenic polymer, the amount of additional α-olefin is less than 50%; other embodiments include at least 0.5 mole percent (mol %) to 25 mol %; In a further embodiment, the amount of additional α-olefin comprises at least 5 mol % to 10 mol %. In some embodiments, the additional α-olefin is 1-octene.

Any conventional polymerization method may be used to prepare the ethylene-based polymer. Such conventional polymerization methods may include, for example, one or more conventional reactors such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors in parallel, series or any combination thereof. solution polymerization methods, gas phase polymerization methods, slurry phase polymerization methods, and combinations thereof using

In one embodiment, the ethylene-based polymer may be prepared via solution polymerization in a dual reactor system, eg, a dual loop reactor system, wherein ethylene and optionally one or more α-olefins are combined in a catalyst system as described herein. and optionally one or more cocatalysts. In another embodiment, the ethylene-based polymer may be prepared via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more α-olefins are combined as described herein and in this disclosure. The polymerization is carried out in the presence of a catalyst system and optionally one or more other catalysts. Catalyst systems as described herein may be used in either the first reactor or the second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer can be prepared via solution polymerization in a dual reactor system, eg, a dual loop reactor system, wherein ethylene and optionally one or more α-olefins are combined as described herein in both reactors. polymerized in the presence of a catalyst system as described above.

In another embodiment, the ethylene-based polymer may be prepared via solution polymerization in a single reactor system, eg, a single loop reactor system, wherein ethylene and optionally one or more α-olefins are combined in a catalyst system as described in this disclosure. and optionally one or more co-catalysts as described in the previous paragraphs.

The ethylene-based polymer may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymer may contain any amount of additives. The ethylene-based polymer may compromise from about 0% to about 10% by weight of the combined weight of such additives, based on the weight of the ethylene-based polymer and one or more additives. The ethylene-based polymer may further include fillers, which may include, but are not limited to, organic or inorganic fillers. The ethylene-based polymer may contain from about 0 to about 20 weight percent of a filler such as, for example, calcium carbonate, talc or Mg(OH) ₂ , based on the combined weight of the ethylene-based polymer and any additives or fillers. The ethylenic polymer may be further blended with one or more polymers to form a blend.

In some embodiments, a polymerization method for preparing an ethylene-based polymer may comprise polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, the catalyst system comprising at least one of Formula (I) of metal-ligand complexes. Polymers obtained from such catalyst systems comprising metal-ligand complexes of formula (I) are for example 0.850 g/cm ³ to 0.950 g/cm ³ , 0.880 g/cm ³ to 0.920 g/cm ³ , 0.880 g/cm cm ³ to 0.910 g/cm ³ or 0.880 g/cm ³ to 0.900 g/cm ³ in accordance with ASTM D792, which is incorporated herein by reference in its entirety.

In another embodiment, the polymer obtained from a catalyst system comprising a metal-ligand complex of formula (I) has a melt flow ratio (I ₁₀ /I ₂ ) of 5 to 15, wherein the melt index I ₂ is 190°C and Measured according to ASTM D1238 at a load of 2.16 kg, which is incorporated herein by reference in its entirety, and the melt index I ₁₀ is measured according to ASTM D1238 at 190° C. and a load of 10 kg. In other embodiments, the melt flow ratio (I ₁₀ /I ₂ ) is between 5 and 10, and in other embodiments, the melt flow ratio is between 5 and 9.

In some embodiments, the polymer obtained from a catalyst system comprising a metal-ligand complex of formula (I) has a molecular-weight distribution (MWD) of 1 to 25, wherein MWD is M _w /M _n . defined, wherein M _w is the weight-average molecular weight and M _n is the number-average molecular weight. In another embodiment, the polymer obtained from the catalyst system has a MWD of 1 to 6. other embodiments include MWD of 1 to 3; Other embodiments include a MWD of 1.5 to 2.5.

Embodiments of the catalyst systems described in this disclosure obtain unique polymer properties as a result of the high molecular weight of the resulting polymer and the amount of comonomer incorporated into the polymer.

All solvents and reagents were obtained from commercial suppliers and used as received, unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran and diethyl ether are purified by passing through activated alumina and, in some cases, a Q-5 reactant. The solvent used in the experiments performed in a nitrogen-filled glovebox was stored on activated 4 Å molecular sieves for further drying. Glass containers for moisture-sensitive reactions are dried in an oven overnight before use. NMR spectra are recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis is performed using a Waters e2695 separation module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector and a Waters 3100 ESI mass detector. LC-MS separations are performed on an XBridge C18 3.5 μm 2.1×50 mm column using an acetonitrile to water gradient from 5:95 to 100:0 with 0.1% formic acid as ionizer. HRMS analysis is performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 μm 2.1×50 mm column coupled with an Agilent 6230 TOF mass spectrometer with electrospray ionization. ¹ H NMR data are reported as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = hexant, sept = triplet and m = multiplet), integral and assignment). Chemical shifts to ¹ H NMR data are reported as downfield in ppm from internal tetramethylsilane (TMS, δ scale) using residual protons in deuterated solvent as reference. ¹³ C NMR data are determined using ¹ H decoupling, chemical shifts reported downfield in ppm from tetramethylsilane (TMS, δ scale) compared using residual carbon in deuterated solvent as reference.

General Procedure for PPR Screening Experiments

Polyolefin catalysis screening is performed in a high throughput parallel polymerization reactor (PPR) system. The PPR system consists of 48 multiple single cell (6 x 8 matrix) reactors in a glovebox with an inert atmosphere. Each cell is equipped with a glass insert having an internal working liquid volume of about 5 mL. Each cell independently controls the pressure, and the liquid in the cell is continuously stirred at 800 rpm. Catalyst solutions are prepared by dissolving an appropriate amount of the procatalyst in toluene, unless otherwise stated. All liquids (eg, solvent, 1-octene, chain shuttling agent solution and catalyst solution appropriate for the experiment) are added to the single cell reactor via a robotic syringe. The gaseous reactant (ie, ethylene, H ₂ ) is added to the single cell reactor through a gas inlet port. The reactor is heated to 80° C. before each run, purged with ethylene and then evacuated.

A portion of Isopar-E is added to the reactor. The reactor is heated to run temperature and pressurized to the appropriate psig with ethylene. A toluene solution of the reactants is added in the following order: (1) 1-octene with 500 nmol of scavenger MMAO-3A; (2) activators (cocatalyst-1, cocatalyst-2, etc.); and (3) a catalyst.

Add a small amount of Isopar-E after each liquid addition so that the total reaction volume reaches 5 mL after the last addition. Immediately after the addition of the catalyst, the PPR software starts monitoring the pressure of each cell. The pressure (within about 2-6 psig) is maintained by opening a valve for less than 1 psi of the set point to add supplemental ethylene gas and closing it when a pressure greater than 2 psi is reached. All pressure drops are recorded cumulatively as "uptake" or "conversion" of ethylene over the duration of the run or until the required uptake or conversion value, whichever occurs first, is reached. Each reaction is quenched by addition of 10% carbon monoxide in argon for 4 minutes at a pressure of 40-50 psi above the reactor pressure. A shorter "quench time" means that the catalyst is more active. The reaction is quenched when a predetermined absorption level (50 psig run at 120° C., 75 psig run at 150° C.) is reached to avoid creating too much polymer in any given cell. After all reactions have been quenched, the reactor is allowed to cool to 70°C. Vent the reactor and purge with nitrogen for 5 minutes to remove carbon monoxide and remove the tube. The polymer sample is dried at 70° C. for 12 hours in a centrifugal evaporator, weighed to determine the polymer yield, and subjected to IR (1-octene incorporation) and GPC (molecular weight) analysis.

SymRAD HT-GPC analysis

Molecular weight data are determined by analysis on a hybrid Symyx/Dow construction robot-assisted dilution high temperature gel permeation chromatograph (Sym-RAD-GPC). Polymer samples were dissolved by heating to 160° C. for 120 minutes in 10 mg/mL concentration of 1,2,4-trichlorobenzene (TCB) stabilized with 300 parts per million (ppm) butylated hydroxyl toluene (BHT). make it Each sample was diluted to 1 mg/mL immediately before injection of 250 μL aliquots of the samples. The GPC is equipped with two Polymer Labs PLgel 10 µm MIXED-B columns (300 x 10 mm) at 160 °C with a flow rate of 2.0 mL/min. Sample detection is performed using a PolyChar IR4 detector in concentration mode. A conventional calibration of a narrow polystyrene (PS) standard was performed at this temperature with apparent units adjusted for homo-polyethylene (PE) using the known Mark-Houwink coefficients for PS and PE in TCB. use together

1-octene incorporation IR analysis

HT-GPC analysis of the sample is performed prior to IR analysis. For IR analysis, a 48-well HT silicon wafer is used for deposition of the sample and analysis of 1-octene incorporation. For analysis, samples were heated to 160° C. for up to 210 minutes; The sample is reheated to remove the magnetic GPC stir bar and shaken with a glass bar stir bar on a J-KEM Scientific heated robotic shaker. Samples are deposited with heating using a Tecan MiniPrep 75 deposition station, and 1,2,4-trichlorobenzene is evaporated from the deposited wells of the wafer at 160° C. under a nitrogen purge. The analysis of 1-octene is described in NEXUS 670 E.S.P. Performed on HT silicon wafers using FT-IR.

Batch Reactor Polymerization Procedure

Batch Reactor The polymerization reaction is carried out in a 4 L Parr™ batch reactor. The reactor is heated with an electric heating mantle and cooled with an internal serpentine cooling coil containing cooling water. The reactor and heating/cooling system are both controlled and monitored by a Camile™ TG process computer. The bottom of the reactor is equipped with a dump valve that empties the reactor contents into a stainless steel dump pot. The dump pot is pre-filled with catalyst kill solution (typically 5 mL of an Irgafos/Irganox/toluene mixture). The dump port is evacuated to a 30 gallon blow-down tank and both the port and tank are purged with nitrogen. All solvents used for polymerization or catalyst construction are passed through a solvent purification column to remove any impurities that may affect polymerization. The 1-octene and IsoparE are passed through two columns, a first column containing A2 alumina and a second column containing Q5. Ethylene is passed through two columns, a first column containing A204 alumina and 4 A molecular sieve and a second column containing Q5 reactant. The N ₂ used for transfer is passed through a single column containing A204 alumina, 4 Å molecular sieves and Q5.

The reactor is first loaded from a shot tank which may contain IsoparE solvent and/or 1-octene depending on the reactor load. The short tank is filled to the load set point using a laboratory scale mounted on the short tank. After addition of the liquid feed, the reactor is heated to the polymerization temperature set point. If ethylene is used, it is added to the reactor when the ethylene is at the reaction temperature to maintain the reaction pressure set point. The amount of ethylene added is monitored with a micro-motion flow meter. For some experiments, standard conditions at 120° C. are 88 g ethylene and 568 g 1-octene in 1155 g IsoparE, and standard conditions at 150° C. are 81 g ethylene in 1043 g IsoparE and 570 g It is 1-octene.

The procatalyst and activator are mixed with an appropriate amount of purified toluene to obtain a molar solution. The procatalyst and activator are treated in an inert glovebox and transferred under pressure to the catalyst shot tank by suction with a syringe. The syringe is rinsed three times with 5 mL of toluene. Immediately after adding the catalyst, the run timer is started. If ethylene is used, it is added by Camile to maintain the reaction pressure set point in the reactor. After the polymerization reaction has run for 10 minutes, the stirrer is stopped and the lower dump valve is opened to empty the reactor contents into the dump port. The contents of the dump pot were poured into trays and placed in a laboratory hood to evaporate the solvent overnight. The tray containing the residual polymer is transferred to a vacuum oven, which is heated under vacuum below 140° C. to remove any residual solvent. Efficiency was measured by weighing the polymer for yield after the tray was cooled to ambient temperature and subjected to polymer testing.

Example

Examples 1-45 are synthetic procedures for ligand intermediates, ligands, and isolated procatalysts. The structures of Ligands 1-17 are shown in Figures 3-5. Procatalysts 1 to 74 were synthesized from ligands 1 to 17. A general synthetic scheme is illustrated, and one or more features of the present disclosure are illustrated in view of the following examples:

Example 1 Synthesis of Monocarbodiimide Intermediate for Ligand 1

To a solution of benzylisothiocyanate (2.00 mL, 15.079 mmol, 1.00 equiv) in CH ₂ Cl ₂ (50 mL) was carefully added via syringe cyclohexylamine (1.70 mL, 15.079 mmol, 1.00 equiv). After stirring (300 rpm) at 23° C. for 24 hours, EtOH (50 mL) was added, followed by iodomethane (1.40 mL, 22.620 mmol, 2.00 equiv). After stirring at 23° C. for 24 hours, a clear pale yellow solution was neutralized with a saturated aqueous mixture (50 mL) of NaHCO ₃ , and then aqueous NaOH (15 mL, 1 N) was added to form a biphasic mixture (biphasic). mixture) was stirred vigorously (1000 rpm) for 2 minutes, poured into a separatory funnel, separated, and the organics were washed with a saturated aqueous mixture of NaHCO ₃ (3 x 25 mL), and the remaining organics were CH ₂ Cl ₂ (2 x 20 mL) was used to extract them from the aqueous layer and combine them, dried over solid Na ₂ SO ₄ , transferred and concentrated to give crude methylisothiourea (3.740 g, 14.252 mmol, 95%) as a clear golden yellow oil (clear golden yellow). oil) was obtained. NMR showed the product present as a complex mixture of isomers. The crude material was used in the subsequent reaction without purification.

The above crude isothiourea (3.740 g, 14.252 mmol, 1.00 equiv) and Et ₃ N (1.586 g, 2.20 mL) in MeCN-CH ₂ Cl ₂ (150 mL, 1:1) in an oven dried brown bottle at 23° C. , 15.677 mmol, 1.10 equiv) of solid AgNO ₃ (2.542 g, 14.965 mmol, 1.05 equiv) was added all at once to a clear golden solution. After stirring for 2 hours (500 rpm), the canary yellow heterogeneous mixture was removed, diluted with hexane (100 mL), and vigorously stirred (1000 rpm) for 2 minutes, followed by suction filtration on a celite pad, Washed with hexanes (3 × 25 mL), concentrated to about 10 mL, and concentrated to about 10 mL of a dark yellow material by addition of hexane (25 mL), this process was repeated two more times to obtain residual MeCN and CH ₂ Cl ₂ was removed, the residual silver and ammonium salts were triturated, and the obtained dark tan heterogeneous mixture was diluted with hexane (25 mL), filtered with suction through a pad of celite, washed with hexane (3 x 25 mL) Concentration afforded monocarbodiimide (2.510 g, 11.712 mmol, 82%) as a clear pale yellow oil. NMR showed the product.

Characterization of Thiourea:

¹ H NMR (500 MHz, chloroform- d ) δ 7.39 - 7.27 (m, 5H), 6.16 (br s, 1H), 5.79 (br s, 1H), 4.61 (br s, 2H), 3.80 - 3.90 (m , 1H), 1.94 (dq, J = 12.6, 4.0 Hz, 2H), 1.64 (dt, J = 13.8, 3.9 Hz, 2H), 1.56 (dq, J = 12.2, 4.0 Hz, 1H), 1.37 - 1.27 ( m, 2H), 1.14 (tt, J = 15.3, 7.6 Hz, 3H). ¹³ C NMR (126 MHz, chloroform- d ) δ 180.54, 136.88, 128.92, 127.92, 127.54, 52.96, 48.38, 32.69, 25.31, 24.51.

Characterization of methylisothiourea:

¹ H NMR (500 MHz, chloroform- d ) δ 7.34 (dt, J = 14.8, 7.6 Hz, 4H), 7.23 (t, J = 7.3 Hz, 1H), 4.70 - 4.30 (m, 2H), 4.25 - 3.90 (m, 1H), 3.90 - 3.40 (m, 1H), 2.38 (s, 3H), 2.09 - 1.80 (m, 2H), 1.72 (dt, J = 13.4, 4.1 Hz, 2H), 1.62 (dt, J ) = 13.0, 4.0 Hz, 1H), 1.37 (q, J = 12.5 Hz, 2H), 1.20 (q, J = 12.2 Hz, 3H). ¹³ C NMR (126 MHz, chloroform- d ) δ 150.83, 141.74, 128.23, 127.35, 126.42, 54.16, 50.70, 34.61, 25.81, 24.92, 14.44. HRMS (ESI): C ₁₅ H ₂₂ N ₂ S [M+H] ⁺ Estimated 263.1577; Found 263.1555.

Characterization of monocarbodiimides:

¹ H NMR (500 MHz, chloroform- d ) δ 7.38 - 7.24 (m, 5H), 4.35 (s, 2H), 3.15 (dp, J = 8.3, 3.8 Hz, 1H), 1.72 (ddt, J = 56.9, 13.0, 4.0 Hz, 4H), 1.55 - 1.48 (m, 1H), 1.31 - 1.09 (m, 5H). ¹³ C NMR (126 MHz, chloroform- d ) δ 140.72, 138.70, 128.55, 127.68, 127.43, 55.68, 50.72, 34.68, 25.37, 24.48. HRMS (ESI): C ₁₄ H ₁₈ N ₂ [M+H] ⁺ estimated 215.1543; Found 215.1536.

Example 2: Synthesis of Ligand 1

To a solution of Et ₂ NH (5.0 mL) in anhydrous deoxygenated THF (5.0 mL) in a nitrogen filled glovebox at 22° C. was added one drop of a solution of carbodiimide (90.0 mg, 0.4200 mmol, 1.00 equiv) in THF (0.90 mL). were added slowly. After stirring (300 rpm) for 24 hours, the clear colorless solution was concentrated and concentrated by suspending in hexane (3 mL). This suspension/concentration process was repeated three more times to remove residual Et ₂ NH, and insoluble impurities were crushed. The white amorphous solid was suspended in hexane (5 mL), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 2 minutes, washed with hexane (3 x 5 mL), and concentrated to guanidine (0.109 g) , 0.3792 mmol, 90%) as a clear pale yellow amorphous oil. NMR showed the product present as a complex mixture of isomers and tautomers.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.56 (d, J = 7.5 Hz, 2H), 7.25 (t, J = 7.6 Hz, 2H), 7.11 (d, J = 10.5 Hz, 1H), 4.45 - 4.30 (m, 2H), 3.19 (q, J = 7.1 Hz, 4H), 3.25 - 3.00 (m, 2H), 1.84 - 1.31 (m, 4H), 1.06 (q, J = 13.4, 10.2 Hz, 10H) ), 0.81 (dq, J = 74.8, 12.2 Hz, 2H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 155.66, 143.13, 128.11, 125.95, 53.42, 51.62, 42.74, 34.50, 25.49, 25.31, 24.89, 12.66.

Example 3: Synthesis of Ligand 2

To a solution of pyrrolidine (3.0 mL) in anhydrous deoxygenated THF (2.5 mL) in a nitrogen-filled glovebox at 22° C. was added one drop of a solution of carbodiimide (50.0 mg, 0.2333 mmol, 1.00 equiv) in THF (0.50 mL). were added slowly. After stirring (300 rpm) for 24 hours, the clear colorless solution was concentrated, suspended in hexane (3 mL), and concentrated, and this suspension/concentration process was repeated three more times to remove residual pyrrolidone, and insoluble impurities were crushed. The white amorphous solid was suspended in hexane (5 mL), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 2 minutes, washed with hexane (3 x 5 mL), and concentrated to guanidine (55.5 mg , 0.1944 mmol, 83%) as a clear pale yellow amorphous oil. NMR showed the product present as a complex mixture of isomers and hydrogen bond tautomers/isomers.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.62 (d, J = 7.4 Hz, 2H), 7.27 (t, J = 7.6 Hz, 2H), 7.20 - 7.05 (m, 1H), 4.55 - 4.35 ( m, 2H), 3.45 - 3.27 (m, 4H), 3.26 - 3.17 (m, 1H), 3.10 - 2.94 (m, 1H), 1.86 - 1.68 (m, 2H), 1.56 - 1.41 (m, 6H), 1.40 - 0.71 (m, 6H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 154.99, 143.50, 128.07, 127.93, 125.90, 53.14, 51.67, 48.12, 34.74, 25.51, 25.30, 25.14.

Example 4: Synthesis of Ligand 3

A solution of diisopropylamine (5.0 mL) and carbodiimide (35.0 mg, 0.1633 mmol, 1.00 equiv) was placed in a mantle heated to 85 °C, stirred for 48 hours (300 rpm), and the clear colorless solution was concentrated and hexane ( 3 mL) and concentrated, this suspension/concentration process was repeated three more times to remove residual diisopropylamine , insoluble impurities were pulverized, and white amorphous solid was suspended in hexane (5 mL) for 2 minutes. Filtration through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) during NMR showed the product present as a complex mixture of isomers and tautomers. (*) indicates the chemical shift of the hydrophobic isomer.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.58 (d, J = 7.6 Hz, 2H), 7.24 (p, J = 11.4, 9.4 Hz, 2H), 7.10 (d, J = 16.5 Hz, 1H) , (4.88 - 4.67 (m, 2H)*) 4.43 - 4.33 (m, 2H), (4.06 - 3.92 (m, 1H)*) 3.67 - 3.49 (m, 2H), 3.07 (br s, 1H) 3.01 - 2.86 (m, 1H), 2.15 - 1.86 (m, 2H), 1.86 - 1.35 (m, 4H), 1.27 (dd, J = 22.4, 6.7 Hz, 12H), 1.29 - 1.20 (m, 2H), 1.13 - 0.69 (m, 2H), (0.97 - 0.90 (m, 12H)*). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 155.13, 143.25, 128.10, 127.09, 125.90, (53.52*) 51.95, 49.37, 47.62 (46.99*), 34.65 (33.25*), (26.10*) 25.47 (24.92) *), 21.81, 20.98.

Example 5: Synthesis of Ligand 4

To a solution of pyrrole (16.0 µL, 0.2333 mmol, 1.00 equiv) in anhydrous deoxygenated THF (2 mL) in a nitrogen-filled glovebox at 22 °C (10.0 µL, 0.0233 mmol, 0.10 equiv, 2.40 M titration in hexanes) was slowly and carefully added drop by drop via syringe. After stirring (300 rpm) for 2 minutes, a solution of carbodiimide (50.0 mg, 0.2333 mmol, 1.00 equiv) in THF (0.50 mL) was slowly added dropwise. After stirring for 24 hours, the pale yellow solution was concentrated and suspended in hexane (5 mL), and this suspension/concentration process was repeated three more times to remove residual THF and pyrrole, and the obtained opaque mixture was concentrated in hexane (5 mL) ), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with hexane (3 x 5 mL) and concentrated to give guanidine (55.5 mg, 0.1972 mmol, 85%) to a clear pale yellow color. Obtained as an amorphous oil. NMR showed the product present as a complex mixture of isomers and tautomers.

The product exists as a complex mixture of isomers and tautomers: (*) indicates the minor isomer.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.40 - 7.30 (m, 2H), 7.29 - 6.92 (m, 3H), 6.69 - 6.58 (br s, 2H), 6.25 - 6.14 (br s, 2H) , 4.50 - 4.32 (br s, 2H) (4.26 (s, 2H)*), (3.76 (s, 1H)*) 3.61 - 3.43 (br s, 2H), 3.30 - 3.13 (m, 1H), 1.98 - 1.83 (m, 2H), 1.73 - 1.16 (m, 4H), 1.16 - 1.04 (m, 2H), 0.99 - 0.53 (m, 2H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 142.41, (128.31*) 128.14, (127.10*) 126.08, 119.74, (110.09*) 109.26, 52.26, 50.02, (35.64*) (34.41*) 32.53, 25.74 , 24.73.

Example 6: Synthesis of Ligand 5

Titration of n-BuLi (5.0 μL, 0.0166 mmol, 0.05 equiv, 2.40 M in hexanes) to a solution of imidazole (15.9 mg, 0.2333 mmol, 1.00 equiv) in anhydrous deoxygenated THF (2 mL) at 22 °C in a nitrogen-filled glovebox. ) was slowly and carefully added drop by drop via syringe. After stirring (300 rpm) for 2 minutes, a solution of carbodiimide (50.0 mg, 0.2333 mmol, 1.00 equiv) in THF (0.50 mL) was slowly added dropwise. After stirring for 48 h, the pale yellow solution was concentrated and concentrated by suspending in PhH-hexane (5 mL, 1:1), and this suspension/concentration procedure was repeated three more times to remove residual THF and pyrrolidine, yielded The resulting opaque mixture was suspended in PhH-hexane (5 mL, 1:1), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, and PhH-hexane (3 x 5 mL, 1:1) ) and concentrated to give guanidine (63.9 mg, 0.2263 mmol, 95%) as a clear pale yellow amorphous oil. NMR showed the product present as a mixture of isomers and tautomers.

The product exists as a complex mixture of isomers and tautomers: (*) indicates the minor isomer.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.26 (d, J = 7.8 Hz, 2H), 7.19 - 6.95 (m, 5H), 6.57 - 6.48 (m, 1H), 4.23 - 4.14 (br s, 2H), 3.70 (br s, 1H), 3.00 - 2.80 (m, 1H), 1.91 (m, 2H), 1.66 - 1.28 (m, 4H), 1.19 - 0.76 (m, 4H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 141.65, 141.12, 135.57, 129.09, (128.29*) 128.20 (128.15*), (127.52*), 126.96, 126.27, 117.68, (56.30*) 52.13, 50.25 ( 45.91*), 35.40, 32.37, 25.69, 24.75 (24.23*).

Example 7: Synthesis of Ligand 6

Titration of n-BuLi (10.0 μL, 0.0233 mmol, 0.10 equiv, 2.40 M in hexanes) to a solution of pyrazole (15.9 mg, 0.2333 mmol, 1.00 equiv) in anhydrous deoxygenated THF (2 mL) at 22 °C in a nitrogen-filled glovebox. ) was slowly and carefully added drop by drop via syringe. After stirring (300 rpm) for 2 minutes, a solution of carbodiimide (50.0 mg, 0.2333 mmol, 1.00 equiv) in THF (0.50 mL) was slowly added dropwise. After stirring for 48 hours, the pale yellow solution was concentrated and suspended in hexane (5 mL), and this suspension/concentration process was repeated three more times to remove residual THF and pyrazole, and the obtained opaque mixture was concentrated in hexane (5 mL). mL), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with hexanes (3 x 5 mL) and concentrated to give guanidine (58.6 mg, 0.2075 mmol, 89%) a clear Obtained as a colorless amorphous oil. NMR showed the product present as a complex mixture of isomers and tautomers.

The product exists as a complex mixture of isomers and tautomers: (*) indicates the minor isomer.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 8.42 (d, J = 2.6 Hz, 1H), 7.46 (d, J = 7.5 Hz, 2H), 7.38 - 6.95 (m, 3H), 6.22 (d, J = 9.8 Hz, 1H), 6.03 - 5.91 (m, 1H) (5.91 - 5.80 (m, J = 4.6, 2.4 Hz, 1H)*), (4.90 - 4.76 (d, J = 15.2 Hz, 2H)* ) 4.64 (s, 2H), 4.58 - 4.38 (m, 1H), (4.18 - 4.10 (m, J = 6.0 Hz, 1H)*), (3.62 - 3.49 (m, 1H)*) 3.48 - 3.32 (m , 1H), 2.08 - 1.83 (m, 2H), 1.83 - 0.74 (m, 8H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 143.90, 142.03, (139.77*) 139.74, 129.61, 128.19, 127.26, 126.31, 107.39 (106.16*), (51.99*) 51.28, 33.81, (25.74*) 25.25 , (24.59*) 24.20.

Example 8: Synthesis of Ligand 7

To a solution of indole (27.3 mg, 0.2333 mmol, 1.00 equiv) in anhydrous deoxygenated THF (2 mL) in a nitrogen-filled glovebox at 22 °C (5.0 μL, 0.0166 mmol, 0.05 equiv, 2.40 M titration in hexanes) was slowly and carefully added drop by drop via syringe. After stirring (300 rpm) for 2 minutes, a solution of carbodiimide (50.0 mg, 0.2333 mmol, 1.00 equiv) in THF (0.50 mL) was slowly added dropwise. After stirring for 48 hours, the pale yellow solution was concentrated and concentrated by suspending in hexane (5 mL). This suspension/concentration process was repeated three more times to remove residual THF and pyrrolidine, and the obtained opaque mixture was mixed with hexane ( 5 mL), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with hexanes (3 x 5 mL) and concentrated to give guanidine (73.6 mg, 0.2221 mmol, 95%) It was obtained as a clear pale yellow amorphous foam. NMR showed that the product exists as a complex mixture of isomers and tautomers.

The product exists as a complex mixture of isomers and tautomers: (*) indicates the minor isomer.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.62 - 7.52 (m, 1H), 7.44 - 7.30 (br s, 1H), 7.30 - 7.06 (m, 6H), 7.06 - 6.98 (m, 1H), 6.85 - 6.71 (br s, 1H), 6.49 - 6.31 (br s, 1H), 4.35 - 4.07 (br s, 2H), (3.99 - 3.72 (m, 1H)*), 3.72 - 3.38 (m, 1H) , 3.10 - 2.73 (m, 1H), 2.09 - 1.74 (m, 2H), 1.74 - 0.61 (m, 8H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 141.97, 135.45, 128.14, 127.93, 127.17, 126.17, 125.88, 123.06, 122.91, 121.08, 120.94, 111.32, 103.54, (56.36*) 52.36, 50.32 (46.12*)32 (46.12*) , (35.52*) (34.07*) 32.63, (26.83*) 25.57, 24.73, (24.23*).

Example 9: Synthesis of Ligand 8

Titration of n-BuLi (10.0 μL, 0.0233 mmol, 0.10 equiv, 2.40 M in hexanes) to a solution of carbazole (39.0 mg, 0.2333 mmol, 1.00 equiv) in anhydrous deoxygenated THF (2 mL) in a nitrogen-filled glovebox at 22 °C. ) was slowly and carefully added drop by drop via syringe. After stirring (300 rpm) for 2 minutes, a solution of carbodiimide (50.0 mg, 0.2333 mmol, 1.00 equiv) in THF (0.50 mL) was slowly added dropwise. After stirring for 48 hours, the pale yellow solution was concentrated, suspended in hexane (5 mL), and concentrated, and this suspension/concentration process was repeated three more times to remove residual THF, insoluble impurities were crushed, and the obtained opaque mixture was Suspended in hexanes (5 mL), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with hexanes (3 x 5 mL), concentrated to guanidine (72.3 mg, 0.1887 mmol, 81%) ) as an amorphous yellow oil. NMR showed the product present as a complex mixture of isomers and tautomers.

The product exists as a mixture of complex isomers: (*) indicates minority isomers.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 8.01 - 7.82 (m, 2H), 7.43 - 7.29 (m, 2H), 7.29 - 7.23 (m, 3H), 7.22 - 6.94 (m, 6H), 4.32 - 4.10 (br s, 2H) (4.05 - 3.84 (br s, 2H)*), 3.61 - 3.37 (br s, 1H), 3.07 - 2.82 (br s, 1H), 2.15 - 1.84 (m, 2H), 1.80 - 0.66 (m, 8H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 141.92, 139.10, 127.74, 127.51, 126.94, 126.34, 126.01, 123.20, 120.39, 120.27, 110.55, (56.67*) 52.66, 50.23 (46.15*), (35.48*) ) 32.65, 25.67, 24.80.

Example 10: Synthesis of Ligand 9

Titration of n-BuLi (60.0 μL, 0.1585 mmol, 0.10 equiv, 2.61 M in hexanes) to a solution of carbazole (265.0 mg, 1.585 mmol, 1.00 equiv) in anhydrous deoxygenated THF (5 mL) in a nitrogen-filled glovebox at 23 °C. ) was slowly and carefully added drop by drop via syringe. After stirring (300 rpm) for 2 minutes, a solution of carbodiimide (200.0 mg, 0.25 mL, 1.585 mmol, 1.00 equiv) in THF (5 mL) was slowly added dropwise. After stirring for 48 hours, the pale yellow solution was concentrated, suspended in hexane (5 mL), and concentrated, and this suspension/concentration process was repeated three more times to remove residual THF, insoluble impurities were crushed, and the obtained opaque mixture was Suspended in hexanes/PhH (5 mL, 2:1), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with hexanes/PhH (3×5 mL, 2:1) Concentration gave guanidine (317.0 mg, 1.080 mmol, 68%) as an amorphous pale yellow foam. NMR showed the product present as a complex mixture of isomers and tautomers.

The product exists as a mixture of complex isomers: only chemical shifts of the major isomers are described.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 8.01 - 7.85 (m, J = 7.7 Hz, 2H), 7.46 - 7.24 (m, 4H), 7.23 - 7.13 (m, 2H), 4.35 - 3.95 (br s, 1H), 3.44 - 3.17 (m, 1H), 3.17 - 2.93 (br s, 1H), 1.18 - 0.74 (m, 12H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 139.46, 128.17, 126.28, 122.98, 120.42, 120.27, 110.04, 48.94, 42.96, 25.09, 21.94.

Example 11: Synthesis of intermediates for ligands 10 and 11

To a stirred (500 rpm) solution of isothiocyanate (1.85 mL, 12.252 mmol, 1.00 equiv) in Et ₂ O (125 mL) at 23 °C was administered via syringe with benzylamine (1.34 mL, 12.252 mmol, 1.00 equiv). It was carefully added dropwise. After 12 h, the clear colorless solution was concentrated to give thiourea (3.310 g, 12.252 mmol, 100%) as an off-white solid. NMR showed the product, which was used in the subsequent reaction without further purification.

To a stirred (500 rpm) solution of thiourea (3.285 g, 12.149 mmol, 1.00 equiv) in EtOH-CH ₂ Cl ₂ (100 mL, 1:1) in EtOH-CH 2 Cl 2 (100 mL, 1:1) at 23 °C was iodomethane (3.10 mL, 48.596 mmol, 4.00 equiv) ) was carefully added via syringe. After 12 hours the clear pale yellow solution was neutralized with a saturated aqueous mixture of NaHCO ₃ (100 mL), then aqueous NaOH (15 mL, 1 N) was added and the biphasic mixture was vigorously stirred (1000 rpm) for 2 minutes, Separated by pouring into a separatory funnel, the organics were washed with a saturated aqueous mixture of NaHCO ₃ (3 x 50 mL), and the remaining organics were extracted from the aqueous layer using CH ₂ Cl ₂ (2 x 25 mL) and combined, solids It was transferred to dryness over Na ₂ SO ₄ and concentrated to give methylisothiourea (3.450 g, 12.149 mmol, 100%) as a pale yellow oil. This material was used in the subsequent reaction without further purification.

Characterization data of crude methylisothiourea:

¹ H NMR (500 MHz, chloroform- d ) δ 7.36 (d, J = 5.5 Hz, 3H), 7.33 - 7.27 (m, 2H), 7.04 - 6.98 (m, 2H), 6.87 (t, J = 7.5 Hz) , 1H), 4.74 - 4.46 (m, 3H), 2.45 - 2.34 (m, 3H), 2.12 (s, 6H). ¹³ C NMR (126 MHz, chloroform- d ) δ 152.80, 146.31, 138.75, 129.32, 128.63, 127.90, 127.55, 127.45, 122.71, 47.09, 18.07, 13.80.

Characterization data of thiourea:

¹ H NMR (500 MHz, chloroform- d ) δ 7.65 (s, 1H), 7.32 - 7.27 (m, 2H), 7.26 - 7.22 (m, 3H), 7.16 (dd, J = 8.5, 6.5 Hz, 1H) , 7.10 (d, J = 7.5 Hz, 2H), 5.72 - 5.54 (m, 1H), 4.85 (d, J = 5.4 Hz, 2H), 2.26 (s, 6H). ¹³ C NMR (126 MHz, chloroform- d ) δ 181.26, 137.63, 137.30, 132.68, 129.04, 128.67, 127.63, 127.51, 49.17, 18.10.

Example 12: Synthesis of monocarbodiimide intermediates for ligands 10 and 11

A solution of thioguanidine (3.698 g, 13.002 mmol, 1.00 equiv) and Et ₃ N (4.00 mL, 28.604 mmol, 2.20 equiv) in MeCN (130 mL) in an oven-dried brown bottle protected from light was placed in an ice water bath for 30 min. After batching solid AgNO ₃ (4.528 g, 26.654 mmol, 2.05 equiv) was added all at once. After stirring (500 rpm) for 2 hours, hexane (150 mL) was added to the pale yellow heterogeneous mixture, vigorously stirred (1000 rpm) for 2 minutes, filtered with suction over a pad of celite, concentrated to about 10 mL, and hexane (50 mL) was further diluted to about 10 mL, and this process was repeated three more times to remove residual MeCN, the now yellow heterogeneous mixture was diluted with hexane (50 mL) and concentrated by suction filtration over a pad of Celite to mono Carbodiimide (1.781 g, 7.536 mmol, 58%) was obtained as a clear pale yellow oil. NMR showed the product.

¹ H NMR (400 MHz, chloroform- d ) δ 7.39 (d, J = 4.3 Hz, 4H), 7.35 - 7.29 (m, 1H), 7.00 (d, J = 7.9 Hz, 2H), 6.93 (dd, J ) = 8.5, 6.3 Hz, 1H), 4.55 (s, 2H), 2.26 (s, 6H). ¹³ C NMR (101 MHz, chloroform- d ) δ 138.04, 136.34, 134.33, 132.32, 128.67, 128.07, 127.62, 127.50, 124.27, 50.57, 18.84.

Example 13: Synthesis of Ligand 10

Titration of n-BuLi (25.0 μL, 0.0609 mmol, 0.10 equiv, 2.50 M in hexanes) to a solution of carbazole (0.144 g, 0.6094 mmol, 1.00 equiv) in anhydrous deoxygenated THF (5 mL) in a nitrogen-filled glovebox at 23 °C. ) was slowly and carefully added drop by drop via syringe. After stirring (300 rpm) for 2 min, a solution of carbodiimide (0.102 g, 0.6094 mmol, 1.00 equiv) in THF (5 mL) was slowly added dropwise. After stirring for 48 hours, the pale yellow solution was concentrated and concentrated by suspending in hexane/PhMe (5 mL, 1:1). This suspension/concentration process was repeated three more times to remove residual THF, and insoluble impurities were crushed. , the resulting opaque mixture was suspended in hexane/PhMe (5 mL, 1:1) and filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, hexane/PhH (3×5 mL, 1 :1) and concentration to give guanidine (0.197 g, 0.4875 mmol, 80%) as an amorphous pale yellow foam. NMR showed the product present as a mixture of isomers and tautomers.

The product exists as a mixture of isomers: only chemical shifts of the major isomers are described.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 8.05 - 7.79 (m, 4H), 7.40 - 7.24 (m, 2H), 7.24 - 7.09 (m, 4H), 7.09 - 6.69 (m, 6H), 4.64 - 4.31 (br s, 1H), 3.60 - 3.30 (br s, 2H), 2.15 (s, 6H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 145.15, 139.53, 128.49, 128.32, 128.14, 127.95, 127.25, 126.30, 125.50, 124.41, 123.39, 123.28, 120.99, 120.13, 112.48, 47.76, 18.55.

Example 14: Synthesis of Ligand 11

A solution of carbodiimide (0.144 g, 0.6094 mmol, 1.00 equiv) in anhydrous deoxygenated benzene (1.0 mL) in a solution of Et ₂ NH (5.0 mL) in anhydrous deoxygenated THF (5.0 mL) in a nitrogen filled glovebox at 22 °C was slowly added dropwise. After stirring (300 rpm) for 48 hours, the clear colorless solution was concentrated and concentrated by suspending in hexane (3 mL). This suspension/concentration process was repeated three more times to remove residual Et ₂ NH, and insoluble impurities were crushed. The clear golden foam was suspended in hexane (5 mL), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 2 minutes, washed with hexane (3 x 5 mL), and concentrated to guanidine (0.118 g) , 0.3813 mmol, 63%) as a clear golden amorphous oil. NMR showed the product.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.07 - 7.03 (m, 2H), 7.02 - 6.97 (m, 2H), 6.97 - 6.92 (m, 1H), 6.90 - 6.81 (m, 3H), 3.81 (d, J = 6.4 Hz, 2H), 3.63 - 3.56 (m, 1H), 3.09 (q, J = 7.1 Hz, 4H), 2.16 (s, 6H), 1.00 (t, J = 7.0 Hz, 6H) . ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 152.67, 147.85, 139.70, 129.14, 128.26, 128.14, 126.91, 123.27, 121.47, 48.19, 42.60, 18.50, 12.79.

Example 15: Synthesis of Ligand 12

Titration of n-BuLi (63.0 μL, 0.1585 mmol, 0.10 equiv, 2.50 M in hexanes) to a solution of carbazole (0.265 g, 1.585 mmol, 1.00 equiv) in anhydrous deoxygenated THF (5 mL) in a nitrogen-filled glovebox at 23 °C. ) was slowly and carefully added drop by drop via syringe. After stirring (300 rpm) for 2 minutes, a solution of carbodiimide (0.25 mL, 1.585 mmol, 1.00 equiv) in THF (5 mL) was slowly added dropwise. After stirring for 48 hours, the pale yellow solution was concentrated and concentrated by suspending in hexane/PhMe (5 mL, 1:1). This suspension/concentration process was repeated three more times to remove residual THF, and insoluble impurities were crushed. , the resulting opaque mixture was suspended in hexane/PhMe (5 mL, 1:1) and filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, hexane/PhH (3×5 mL, 1 :1) and concentration to give guanidine (0.395 g, 1.347 mmol, 85%) as an amorphous pale yellow foam. NMR showed the product present as a mixture of isomers and tautomers.

The product exists as a mixture of isomers: only chemical shifts of the major isomers are described.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.92 (dt, J = 7.8, 1.0 Hz, 2H), 7.37 (d, J = 8.2 Hz, 2H), 7.29 (ddd, J = 8.2, 7.1, 1.2 Hz, 2H), 7.15 (ddd, J = 8.1, 7.1, 1.1 Hz, 2H), 3.63 - 3.44 (br s, 1H), 2.93 - 2.75 (m, 2H), 1.24 (s, 9H), 1.01 - 0.90 (m, 3H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 139.49, 139.23, 126.27, 122.94, 120.41, 120.25, 110.31, 50.71, 43.62, 28.21, 17.20.

Example 16: Synthesis of intermediates for ligands 13, 14 and 15

To a vigorously stirred (1000 rpm) solution of isothiocyanate (2.11 mL, 19.77 mmol, 2.00 equiv) in anhydrous ethyl ether (50 mL) at 23 °C under nitrogen was added a solution of cadaverine (1.16 mL, 9.88 mmol, 1.00 equiv). It was carefully added dropwise via syringe over 2 minutes. The clear colorless solution immediately turned into a white heterogeneous mixture, which was concentrated by removing an aliquot after vigorous stirring (1000 rpm) for 12 hours, NMR showed the product. The white mixture was concentrated to give bisthiourea (3.01 g, 9.88 mmol, 100%). NMR showed the product. This material was used in the subsequent reaction without further purification.

¹ H NMR (400 MHz, DMSO- d ₆ ) δ 7.16 (br s, 2H), 7.09 (br s, 2H), 4.18 (br s, 2H), 3.33 - 3.24 (m, 4H), 1.43 (p, J = 7.3 Hz, 4H), 1.21 (tt, J = 8.2, 6.0 Hz, 2H), 1.05 (dd, J = 6.5, 0.9 Hz, 12H). ¹³ C NMR (101 MHz, DMSO- d ₆ ) δ 181.25, 45.21, 43.72, 29.03, 24.29, 22.79. HRMS (ESI): C ₁₃ H ₂₈ N ₄ S ₂ [M+H] ⁺ estimated 305.2255; Found 305.2285.

Example 17: Synthesis of intermediates for ligands 13, 14 and 15

To a mixture of bisthiourea (850.0 mg, 2.79 mmol, 1.00 equiv) in CH ₂ Cl ₂ and ethanol (40 mL, 1:1) at 23° C. was added iodomethane (0.70 mL, 11.16 mmol, 4.00 equiv). The white mixture was stirred (300 rpm) for 12 h, then the now clear colorless homogeneous solution was neutralized with an aqueous saturated mixture of NaHCO ₃ (60 mL) and CH ₂ Cl ₂ (20 mL) to vigorously stir the white mixture for 5 min. After stirring (1000 rpm) an aqueous solution of NaOH (10 mL, 1 N) was added. The now clear colorless biphasic mixture was poured into a separatory funnel, separated and the organics washed with an aqueous saturated mixture of NaHCO ₃ (3×20 mL). Residual organics were combined by back-extraction from aqueous with CH ₂ Cl ₂ (3 x 10 mL), washed with brine (20 mL) and dried over solid Na ₂ SO ₄ , transferred and concentrated to isothio Urea (866.7 mg, 2.61 mmol, 94%) was obtained as an off-white solid. NMR of the solid indicated the product. This material was used in the subsequent reaction without further purification.

¹ H NMR (400 MHz, chloroform- d ) δ 3.82 (br s, 3H), 3.23 (br s, 5H), 2.32 (br s, 6H), 1.57 (p, J = 7.3 Hz, 4H), 1.47 - 1.34 (m, 2H), 1.11 (d, J = 6.3 Hz, 12H). ¹³ C NMR (126 MHz, chloroform- d ) δ 149.84, 46.11, 30.63, 24.95, 23.78, 23.59, 14.35. HRMS (ESI): C ₁₅ H ₃₂ N ₄ S ₂ [M+H] ⁺ Est. 333.2630; Found 333.2634.

Example 18: Synthesis of intermediates for ligands 13, 14 and 15

A solution of bismethylisothiourea (2.363 g, 7.105 mmol, 1.00 equiv) and Et ₃ N (2.10 mL, 14.921 mmol, 2.10 equiv) in non-anhydrous acetonitrile (140 mL) in a brown bottle protected from light was placed in an ice water bath. After placing for 20 minutes, solid AgNO ₃ (2.474 g, 14.565 mmol, 2.05 equiv) was added all at once. After stirring (500 rpm) for 2 hours, the yellow heterogeneous mixture was diluted with hexane (100 mL) and vigorously stirred (1000 rpm) for 2 minutes, cooled by suction filtration through a pad of celite, hexane (4 x 20 mL) ), the resulting golden filtered solution was concentrated to about 10 mL, and concentrated to about 10 mL by adding hexane (50 mL). The silver was triturated, hexanes (50 mL) were added and the mixture was concentrated by suction filtration through a pad of celite to give biscarbodiimide (1.558 g, 6.590 mmol, 93%) as a clear colorless oil. NMR showed the product.

¹ H NMR (500 MHz, chloroform- d ) δ 3.56 (hept, J = 6.4 Hz, 2H), 3.22 (t, J = 6.8 Hz, 4H), 1.68 - 1.51 (m, 4H), 1.51 - 1.37 (m , 2H), 1.22 (d, J = 6.4 Hz, 12H). ¹³ C NMR (126 MHz, chloroform- d ) δ 140.12, 48.91, 46.65, 30.90, 24.59, 24.11. HRMS (ESI): C ₁₃ H ₂₄ N ₄ [M+H] ⁺ estimated 237.2035; Found 237.2027.

Example 19: Synthesis of Ligand 13

To a stirred (300 rpm) solution of Et ₂ NH (5 mL) at 27 °C was slowly added dropwise at 27 °C to a solution of biscarbodiimide (137.4 mg, 0.5813 mmol, 1.00 equiv) in anhydrous deoxygenated THF (2 mL). added. After stirring for 72 hours, the now pale yellow solution was concentrated, hexane (5 mL) was added to concentrate the mixture, and this process was repeated three more times to remove residual Et ₂ NH and insoluble impurities, and a viscous foam was formed with hexane ( 5 mL), filtered through a 0.45 μm ultrafine filter with vigorous stirring (1000 rpm), washed with hexane (3 x 3 mL), and concentrated to give bisguanidine (217.3 mg, 0.5679 mmol, 98%) as a clear It was obtained as a viscous amorphous foam. NMR showed the product present as a complex mixture of isomers and tautomers.

The product exists as a complex mixture of isomers/tautomers: only the major isomers are described.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 3.34 (tdd, J = 12.5, 6.2, 2.3 Hz, 4H), 3.11 (dq, J = 14.0, 7.1, 6.3 Hz, 8H), 2.92 (dd, J ) = 15.4, 9.0 Hz, 2H), 2.66 - 2.55 (m, 2H), 1.87 (p, J = 7.0 Hz, 4H), 1.41 - 1.33 (m, 2H), 1.23 (d, J = 6.1 Hz, 12H) , 1.05 (tt, J = 7.0, 2.3 Hz, 12H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 154.50, 47.90, 45.87, 42.72, 32.55, 25.22, 23.49, 12.65. HRMS (ESI): C ₂₁ H ₄₆ N ₆ [M+H] ⁺ estimated 383.3857; Found 383.3855.

Example 20: Synthesis of Ligand 14

To a stirred (300 rpm) solution of pyrrolidone (5 mL) was slowly added dropwise a solution of biscarbodiimide (137.4 mg, 0.5813 mmol, 1.00 equiv) in anhydrous deoxygenated THF (2 mL) at 27°C. After stirring for 72 hours, the now pale yellow solution was concentrated and the mixture was concentrated by suspending in hexanes (5 mL), this process was repeated three more times to remove residual Et ₂ NH and a viscous foam was formed in hexanes (5 mL). It was suspended in the mixture, stirred vigorously (1000 rpm), filtered through a 0.45 μm ultrafine filter, washed with hexane (3 x 3 mL), and concentrated to give bisguanidine (150.6 mg, 0.3978 mmol, 68%) as a white viscous amorphous It was obtained as a foam. NMR showed the product present as a complex mixture of isomers and tautomers.

The product exists as a complex mixture of isomers/tautomers: only the major isomers are described.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 3.43 - 3.34 (m, 4H), 3.31 (d, J = 6.5 Hz, 8H), 2.94 (q, J = 6.9 Hz, 2H), 1.95 (p, J = 7.1 Hz, 4H), 1.84 (q, J = 7.6 Hz, 4H), 1.75 (t, J = 8.0 Hz, 4H), 1.57 - 1.50 (m, 2H), 1.50 - 1.39 (m, 12H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 154.08, 48.17, 47.98, 45.69, 32.95, 32.43, 25.72, 25.08, 23.77. HRMS (ESI): C ₂₁ H ₄₂ N ₆ [M+H] ⁺ estimated 379.3544; Found 379.3556.

Example 21: Synthesis of Ligand 15

KHMDS (0.20 mL, 0.0985 mmol, 0.20 equiv, non-titration 0.5 M in PhMe) in a solution of carbazole (0.165 g, 0.9850 mmol, 2.00 equiv) in anhydrous deoxygenated THF (2.5 mL) in a nitrogen filled glovebox at 23 °C. solution was added. The now clear pale orange solution was stirred (300 rpm) for 2 minutes, and then a solution of biscarbodiimide (0.116 g, 0.4925 mmol, 1.00 equiv) in THF (2.5 mL) was slowly added dropwise. After stirring (300 rpm) for 72 hours, a clear golden orange solution was concentrated and concentrated by suspending in hexane (3 mL), and this suspension/concentration process was repeated three more times to remove residual THF. , insoluble impurities were triturated, and the pale yellow amorphous solid was suspended in PhH/hexane (5 mL, 1:1) and filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 2 min, PhH/hexane (3 x 5 mL, 1:1) and concentration to give bisguanidine (0.281 g, 0.4914 mmol, 99%) as a clear pale yellow amorphous foam. NMR showed the product present as a complex mixture of isomers and tautomers.

The product exists as a complex mixture of isomers: (*) indicates a minor isomer.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 8.00 - 7.87 (m, 4H), 7.44 - 7.23 (m, 8H), 7.17 (d, J = 8.3 Hz, 4H), 4.33 - 3.92 (m, 2H) ), 3.39 - 3.05 (m, 4H), 3.04 - 2.75 (m, 2H), 1.55 - 1.16 (m, 4H), 1.16 - 1.06 (m, 2H), 1.07 - 0.85 (m, 12H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 141.00, (139.40*) 139.18, 128.19, 126.23, 123.01, (120.39*) 120.36 (120.22*), 110.48, 48.76, 42.95 (41.95*), 31.59, 25.23 , 22.05.

Example 22: Synthesis of intermediates for ligands 16 to 18

To a vigorously stirred (1000 rpm) solution of 2,6-dimethylphenylisothiocyanate (1.85 mL, 12.252 mmol, 2.00 equiv) in Et ₂ O (65 mL) was added cadaverine (0.72 mL, 6.126 mmol, 1.00 equiv). Slowly added dropwise over 1 minute. The clear colorless solution was allowed to stir vigorously at 23° C. for 12 h, then the white heterogeneous mixture was placed in an ice water bath for 1 h to suction filtration cooled, and the white filtered solid was washed with cold Et ₂ O (3 x 20 mL). and dried in vacuo to give bisthiourea (2.331 g, 5.438 mmol, 89%) as a white powder. NMR showed the product.

¹ H NMR (500 MHz, acetone- d ₆ ) δ 8.45 - 8.21 (br s, 1H), 7.19 - 7.04 (m, 6H), 6.64 - 6.27 (br s, 1H), 3.62 - 3.48 (m, 4H) , 2.22 (s, 12H), 1.64 - 1.47 (br s, 4H), 1.36 - 1.16 (br s, 2H). ¹³ C NMR (126 MHz, acetone- d ₆ ) δ 181.44, 137.22, 134.45, 128.35, 127.98, 44.44, 28.91, 23.82, 17.40.

Example 23: Synthesis of intermediates for ligands 16 to 18

To a solution of bisthiourea (2.331 g, 5.438 mmol, 1.00 equiv) in EtOH-CH ₂ Cl ₂ (100 mL, 1:1) at 23 °C was iodomethane (3.087 g, 1.40 mL, 21.752 mmol, 4.00 equiv) added. After stirring (500 rpm) for 12 h, the clear pale yellow solution was neutralized with a saturated aqueous mixture of NaHCO ₃ (100 mL) and then aqueous NaOH (15 mL, 1 N) was slowly added to give a white heterogeneous mixture of the two phases for 2 min. The organics were washed with a saturated aqueous mixture of NaHCO ₃ (3 x 50 mL) and the organics were washed with a saturated aqueous mixture of NaHCO 3 (3 x 50 mL) by pouring into a separatory funnel (1000 rpm) and the remaining organics using CH ₂ Cl ₂ (2 x 25 mL). was extracted from the aqueous layer and combined, washed with brine (1 x 50 mL) and dried over solid Na ₂ SO ₄ , which was transferred and concentrated to give bismethylisothiourea (2.483 g, 5.438 mmol, 100%). . NMR showed the product as a mixture of isomers/tautomers with trace impurities. The crude material was used in the subsequent reaction without further purification.

¹ H NMR (500 MHz, chloroform- d ) δ 7.00 (d, J = 7.5 Hz, 4H), 6.86 (t, J = 7.5 Hz, 2H), 4.40 - 4.13 (br s, 2H), 3.49 - 3.20 ( br s, 4H), 2.51 - 2.27 (br s, 6H), 2.10 (s, 12H), 1.71 - 1.50 (br s, 4H), 1.46 - 1.25 (br s, 2H). ¹³ C NMR (126 MHz, chloroform- d ) δ 152.52, 146.60, 129.25, 127.89, 122.52, 43.01, 29.90, 24.07, 18.01, 13.66.

Example 24: Synthesis of intermediates for ligands 16 to 18

Bismethylisothiourea (2.493 g, 5.459 mmol, 1.00 equiv) and Et ₃ N (3.20) in acetonitrile (110 mL, 1:1) with non-anhydrous CH ₂ Cl ₂ in a brown bottle protected from light at 23 °C. To a stirred (500 rpm) solution of 22.928 mmol, 4.20 equiv) was added solid AgNO3 (3.709 g, 21.836 mmol, 4.00 equiv) all in one portion. After 3.5 hours, the tan heterogeneous mixture was diluted with hexane (100 mL), stirred vigorously (1000 rpm) for 2 minutes, suction filtered through a pad of celite, concentrated to about 10 mL, and hexane (50 mL) was added. Concentrated to about 10 mL, this process was repeated three more times, hexane (50 mL) was added and the mixture was concentrated by suction filtration through a pad of celite to biscarbodiimide (1.575 g, 4.370 mmol, 80%). ) was obtained as a pale golden yellow oil. NMR showed the product.

¹ H NMR (500 MHz, chloroform- d ) δ 7.01 (dq, J = 7.3, 0.7 Hz, 4H), 6.93 (dd, J = 8.2, 6.8 Hz, 2H), 3.40 (t, J = 6.8 Hz, 4H) ), 2.34 (s, 12H), 1.74 - 1.66 (m, 4H), 1.59 - 1.51 (m, 2H). ¹³ C NMR (126 MHz, chloroform- d ) δ 136.80, 133.75, 132.19, 128.12, 124.11, 46.67, 30.72, 24.27, 18.93. HRMS (ESI): C ₂₃ H ₂₈ N ₄ [M+H] ⁺ estimated 361.2314; Found 361.2299.

Example 25: Synthesis of Ligand 16

To a solution of carbazole (39.0 mg, 0.2330 mmol, 2.00 equiv) in anhydrous deoxygenated THF (2.5 mL) in a nitrogen filled glovebox at 23 °C, KHMDS (23.0 µL, 0.0117 mmol, 0.20 equiv, non-titration 0.5 M in PhMe) ) was added. The now clear, pale orange solution was stirred (300 rpm) for 2 minutes and then biscarbodiimide (42.5 mg, 0.1165 mmol, 1.00 equiv) in THF (2.5 mL) was added slowly dropwise. After stirring (300 rpm) for 72 hours, the clear golden-orange solution was concentrated and concentrated by suspending in hexane (3 mL). This suspension/concentration process was repeated three more times to remove residual THF, and insoluble impurities were pulverized. , pale yellow amorphous solid was suspended in PhH/hexane (5 mL, 1:1) and filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 2 min, PhH/hexane (3×5 mL, 1: 1) and concentration to give bisguanidine (67.5 mg, 0.0971 mmol, 84%) as a clear pale yellow amorphous foam. NMR showed the product present as a complex mixture of isomers and tautomers and containing hexane.

The product exists as a complex mixture of isomers: (*) indicates a minor isomer.

¹ H NMR (500 MHz, benzene- d ₆ ) δ (8.04 - 7.88 (m, 4H)*) 7.88 - 7.78 (m, 4H), 7.40 - 7.24 (m, 4H), 7.18 - 7.08 (m, 4H) , 7.09 - 6.97 (m, 6H), 6.97 - 6.85 (m, 4H), 4.33 - 4.07 (m, 2H), 4.04 - 3.76 (br s, 4H), 2.35 - 2.15 (br s, 12H), 2.15 - 1.97 (m, 4H), 1.30 - 1.15 (m, 2H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 145.44, 139.70, 128.59, 128.32, (128.17*), 127.23, 126.30, (125.49*), 124.20 (123.16*), 120.93, (120.27*) 120.22, 112.17 (110.39*), 43.22, 30.44, 25.24, 18.67.

Example 26: Synthesis of Procatalyst 1

To a clear golden-orange solution of ZrBn ₄ (23.8 mg, 0.0512 mmol, 1.00 equiv) in anhydrous deoxygenated C ₆ D ₆ (1.0 mL) at 23 °C in a nitrogen filled glovebox with guanidine in C ₆ D ₆ (0.60 mL) 15.0 mg, 0.0512 mmol, 1.00 equiv) solution was added dropwise. The now canary golden yellow solution was stirred vigorously (1000 rpm) for 1 h, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated and anhydrous deoxygenated hexane ( 3 mL) and concentrated, this suspension/concentration process was repeated two more times to remove residual C ₆ D ₆ and PhMe, and the resulting mixture was suspended in hexane (2 mL) to obtain PhMe (2 mL). The mixture was stirred vigorously (1000 rpm) for 2 minutes, filtered through a 0.20 μm PTFE filter, washed with hexanes/PhMe (3 x 3 mL, 1:1), and the filtrate was concentrated to obtain zirconium complex ( 31.3 mg, 0.0481 mmol, 94%) were obtained as a pale yellow foam. NMR showed the product.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.21 - 7.17 (m, 2H), 7.15 - 7.09 (m, 3H), 7.08 - 7.03 (m, 6H), 6.89 - 6.83 (m, 3H), 6.80 - 6.75 (m, 6H), 4.13 - 4.04 (m, 2H), 3.14 - 3.00 (m, 1H), 2.58 (q, J = 7.1 Hz, 4H), 2.30 (s, 6H), 1.71 (dt, J ) = 30.7, 12.2 Hz, 6H), 1.53 - 1.46 (m, 1H), 1.20 - 0.99 (m, 3H), 0.58 (t, J = 7.0 Hz, 6H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 175.90, 143.85, 141.97, 130.53, 129.21, 128.36, 126.27, 125.76, 122.28, 72.74, 58.53, 51.12, 41.12, 34.64, 26.51, 25.54, 12.61.

Example 27: Synthesis of Procatalyst 3

To a solution of tetrakis-trimethylsilylmethyl zirconium (18.4 mg, 0.0418 mmol, 1.00 equiv) in C ₆ D ₆ (0.38 mL) in a nitrogen filled glovebox at 23° C. was guanidine (12.0 mg) in C ₆ D ₆ (0.24 mL). , 0.0418 mmol, 1.00 equiv) solution was added dropwise. The clear pale yellow solution was stirred (300 rpm) for 1 hour and then an aliquot was removed and NMR showed complete conversion to the desired complex. The solution was concentrated and concentrated by suspending in anhydrous deoxygenated pentane (3 mL), this suspension/concentration process was repeated three more times, and the obtained pale yellow foam was suspended in pentane (3 mL) to give a pale yellow mixture obtained by suspending in pentane (3 mL). It was filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with pentane (3 x 3 mL), and the filtrate was concentrated to give the zirconium complex (22.8 mg, 0.0356 mmol, 85%) a pale yellow amorphous It was obtained as a foam. NMR showed the product.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.31 - 7.28 (m, 2H), 7.20 - 7.14 (m, 2H), 7.01 (t, J = 7.4 Hz, 1H), 4.52 (s, 2H), 3.03 (tt, J = 11.4, 3.8 Hz, 1H), 2.70 (q, J = 7.1 Hz, 4H), 1.89 - 1.78 (m, 2H), 1.74 - 1.64 (m, 2H), 1.63 - 1.43 (m, 4H), 1.09 (d, J = 8.2 Hz, 2H), 1.01 (s, 6H), 0.59 (t, J = 7.1 Hz, 6H), 0.28 (s, 27H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 174.64, 141.89, 128.26, 126.43, 126.22, 65.84, 56.20, 51.93, 41.75, 35.85, 26.01, 25.63, 12.58, 3.05.

Example 28: Synthesis of Procatalyst 4

To a solution of tetrakis-trimethylsilylmethyl hafnium (22.1 mg, 0.0418 mmol, 1.00 equiv) in C ₆ D ₆ (0.44 mL) in a nitrogen filled glovebox at 23° C. was guanidine (12.0 mg) in C ₆ D ₆ (0.24 mL). , 0.0418 mmol, 1.00 equiv) solution was added. The clear pale yellow solution was stirred (300 rpm) for 1 hour and then an aliquot was removed and NMR showed complete conversion to the desired complex. The solution was concentrated and concentrated by suspending in anhydrous deoxygenated pentane (3 mL), this suspension/concentration process was repeated three more times, and the obtained pale yellow foam was suspended in pentane (3 mL) to give a pale yellow mixture obtained by suspending in pentane (3 mL). It was filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with pentane (3 x 3 mL), and the filtrate was concentrated to give the hafnium complex (27.0 mg, 0.0371 mmol, 89%) a pale yellow amorphous It was obtained as a foam. NMR showed the product.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.30 (d, J = 7.5 Hz, 2H), 7.18 (t, J = 7.5 Hz, 2H), 7.02 (t, J = 7.4 Hz, 1H), 4.61 (s, 2H), 3.22 (d, J = 12.1 Hz, 1H), 2.70 (q, J = 7.1 Hz, 4H), 1.82 (m, 2H), 1.68 (m, 2H), 1.60 (m, 2H) , 1.49 (m, 1H), 1.09 (m, 3H), 0.58 (t, J = 7.1 Hz, 6H), 0.48 (s, 6H), 0.31 (s, 27H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 173.68, 141.70, 128.28, 126.50, 126.26, 72.71, 55.92, 51.41, 41.70, 35.71, 26.05, 25.64, 12.59, 3.44.

Example 29: Synthesis of Procatalyst 7

To a solution of tetrakis-trimethylsilylmethyl zirconium (7.7 mg, 0.0174 mmol, 1.00 equiv) in C ₆ D ₆ (0.16 mL) in a nitrogen filled glovebox at 23° C. was added guanidine (10.0 mg) in C ₆ D ₆ (0.20 mL). , 0.0348 mmol, 2.00 equiv) solution was added. The clear pale yellow solution was stirred (300 rpm) for 1 hour and then an aliquot was removed and NMR showed complete conversion to the desired complex. The solution was concentrated and concentrated by suspending in anhydrous deoxygenated pentane (3 mL), this suspension/concentration process was repeated three more times, and the obtained pale yellow foam was suspended in pentane (3 mL) to give a pale yellow mixture obtained by suspending in pentane (3 mL). It was filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with pentane (3 x 3 mL), and the filtrate was concentrated to give the zirconium complex (13.1 mg, 0.0156 mmol, 90%) a pale yellow amorphous It was obtained as a foam. NMR showed the product.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.41 (d, J = 7.5 Hz, 4H), 7.14 - 7.07 (m, 4H), 7.01 (t, J = 7.3 Hz, 2H), 4.67 (s, 4H), 3.22 - 3.08 (m, 2H), 2.85 (q, J = 7.0 Hz, 8H), 1.91 - 1.48 (m, 14H), 1.27 - 1.10 (m, 6H), 0.89 (s, 4H), 0.72 (t, J = 7.0 Hz, 12H), 0.38 (s, 18H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 176.24, 142.93, 128.26, 126.65, 125.94, 56.99, 56.81, 52.46, 41.40, 35.69, 26.44, 12.85, 3.73.

Example 30: Synthesis of Procatalyst 13

To a clear golden-orange solution of ZrBn ₄ (36.1 mg, 0.0792 mmol, 1.00 equiv) in anhydrous deoxygenated C ₆ D ₆ (1.0 mL) in a nitrogen filled glovebox at 23° C. was guanidine in C ₆ D ₆ (1.00 mL) (1.00 mL). 25.0 mg, 0.0792 mmol, 1.00 equiv) solution was added dropwise. The now golden solution was stirred vigorously (1000 rpm) for 1 min, an aliquot was removed, NMR showed complete conversion of the starting material, the solution was concentrated and suspended in anhydrous deoxygenated hexanes (3 mL) After concentration, this suspension/concentration process was repeated two more times to remove residual C ₆ D ₆ and PhMe, the obtained mixture was suspended in hexane (2 mL), PhMe (2 mL) was added, and the mixture was stirred for 2 Filtration through a 0.20 μm PTFE filter with vigorous stirring (1000 rpm) for min, concentrated the filtrate by washing with hexanes/PhMe (3 x 3 mL, 1:1) (52.8 mg, 0.0778 mmol, 98) %) as a pale tan foam. NMR showed the product.

Characterization at 23°C:

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.22 - 7.05 (m, 11H), 6.92 - 6.87 (m, 3H), 6.82 - 6.78 (m, 6H), 4.33 (s, 2H), 3.40 - 3.32 (m, 1H), 3.28 (hept, J = 6.9 Hz, 2H), 2.30 (s, 6H), 1.75 - 1.62 (m, 4H), 1.18 - 0.97 (m, 6H), 0.94 (br s, 12H) .

Characterization at 50°C:

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.16 (dt, J = 15.2, 7.5 Hz, 5H), 7.08 (t, J = 7.6 Hz, 6H), 6.88 (t, J = 7.4 Hz, 3H) , 6.82 - 6.78 (m, 6H), 4.36 (s, 2H), 3.37 (dq, J = 14.2, 6.9, 6.3 Hz, 1H), 3.29 (h, J = 6.8 Hz, 2H), 2.29 (s, 6H) ), 1.72 - 1.62 (m, 3H), 1.55 - 1.47 (m, 1H), 1.20 - 0.99 (m, 6H), 0.94 (d, J = 6.8 Hz, 12H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 178.01, 144.00, 141.64, 129.14, 128.27, 127.86, 126.26, 126.08, 122.35, 74.48, 57.39, 51.00, 49.79, 34.88, 26.29, 25.55, 22.91.

Example 31: Synthesis of Procatalyst 15

To a solution of guanidine ligand (20.2 mg, 0.0640 mmol, 2.00 equiv) in C ₆ D ₆ (1.0 mL) in a nitrogen filled glovebox at 23° C. was added ZrBn ₄ (14.6 mg, 0.0320 mmol) in C ₆ D ₆ (0.58 mL), 1.00 equiv) solution was added. NMR after 1 h of stirring showed complete consumption of the starting ligand. The golden solution was filtered through a 0.20 μm PTFE filter, washed with PhH (3 x 2 mL) and concentrated to give the zirconium complex (27.0 mg, 0.0272 mmol, 85%) as a golden foam. NMR and VT-NMR showed the product present as a rotomeric mixture.

Chemical shifts in VT-NMR at 70° C. are described:

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.31 (d, J = 7.6 Hz, 4H), 7.26 (d, J = 7.5 Hz, 4H), 7.17 (t, J = 7.6 Hz, 4H), 7.08 (t, J = 7.6 Hz, 4H), 6.99 (dq, J = 15.5, 8.5 Hz, 2H), 6.84 (t, J = 7.3 Hz, 2H), 4.56 (s, 4H), 3.45 (p, J = 6.9 Hz, 4H), 3.40 - 3.32 (m, 2H), 2.57 (s, 4H), 1.83 - 1.42 (m, 10H), 1.29 - 1.12 (m, 10H), 1.06 (d, J = 7.0 Hz, 24H) ). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 179.02, 149.03, 142.43, 128.79, 128.04, 128.01, 126.42, 125.74, 120.23, 56.19, 52.10, 50.07, 35.48, 26.36, 25.71, 23.51.

Example 32: Synthesis of Procatalyst 17

To a yellow suspension of ZrCl ₄ (7.0 mg, 0.0301 mmol, 1.00 equiv) in anhydrous deoxygenated PhMe (1.0 mL) in a nitrogen filled glovebox at 23° C. MeMgBr (0.12 mL, 0.3612 mmol, 6.00 equiv, 3.0 M in Et ₂ O) titration) and vigorously stirring (1000 rpm) for 20 seconds, followed by rapid addition dropwise of a solution of guanidine (19.0 mg, 0.0602 mmol, 2.00 equiv) in PhMe (1.0 mL). The now dark brown mixture was stirred vigorously (1000 rpm) for 2 h, then the now black mixture was diluted with anhydrous deoxygenated PhMe/hexanes (4 mL, 1:1) and vigorously stirred (1000 rpm) for 2 min. Filtered through a 0.45 μm PTFE filter, washed with PhMe/hexanes (3 x 3 mL, 1:1), concentrated and the gray mixture concentrated by suspending in hexanes (3 mL), this suspension/concentration procedure repeated twice Further iterations were repeated to remove residual Et ₂ O, insoluble impurities were triturated, and the mixture was suspended in hexanes/PhMe (3 mL, 1:1) and vigorously stirred (1000 rpm) for 2 min through a 0.45 μm PTFE filter. The filtrate was concentrated by filtration, washing with hexane/PhMe (3 x 3 mL, 1:1), and the above-mentioned hexane suspension/concentration procedure was repeated three more times to obtain a pale tan mixture with hexane/PhMe ( 3 mL, 1:1), filtered through a 0.20 μm PTFE filter, washed with hexanes/PhMe (3 x 3 mL, 1:1), and the filtrate was concentrated to give zirconium complex (20.9 mg, 0.0279 mmol, 93) %) as a pale tan foam. NMR showed the product.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.51 - 7.45 (m, 4H), 7.18 - 7.12 (m, 4H), 7.05 - 7.00 (m, 2H), 4.64 (s, 4H), 3.46 - 3.32 (m, 6H), 1.87 (d, J = 12.1 Hz, 4H), 1.81 - 1.67 (m, 6H), 1.60 - 1.53 (m, 2H), 1.34 - 1.07 (m, 8H), 1.02 (d, J = 6.8 Hz, 24H), 0.81 (s, 6H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 176.77, 142.99, 128.01, 126.59, 125.87, 55.98, 51.22, 49.46, 43.65, 35.84, 26.28, 25.93, 23.06.

Example 33: Synthesis of Procatalyst 35

To a solution of tetrakis _- trimethylsilylmethyl zirconium (13.3 mg, _0.0302 mmol, 1.00 equiv) in C ₆ D ₆ (0.26 mL) in a nitrogen filled glovebox at 23° C. , 0.0302 mmol, 1.00 equiv) solution was added dropwise. After stirring for 1.5 h (300 rpm) an aliquot was removed and NMR showed complete conversion of the starting guanidine to the desired zirconium complex. The clear pale yellow solution was concentrated and concentrated by suspending in anhydrous deoxygenated pentane (3 mL), and this suspension/concentration process was repeated three more times to remove residual C ₆ D ₆ , and the obtained pale yellow amorphous foam was pentane (3 mL), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with pentane (3 x 3 mL), and the filtrate was concentrated to give zirconium complex (17.0 mg, 0.0248 mmol, 82) %) as a pale yellow amorphous foam. NMR showed the product.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.54 (d, J = 8.3 Hz, 1H), 7.49 (d, J = 7.9 Hz, 1H), 7.18 (t, J = 7.7 Hz, 1H), 7.07 (t, J = 7.5 Hz, 1H), 7.02 (t, J = 7.5 Hz, 2H), 6.94 (d, J = 7.9 Hz, 3H), 6.77 (d, J = 3.3 Hz, 1H), 6.38 (d) , J = 3.3 Hz, 1H), 4.26 (d, J = 15.1 Hz, 1H), 4.16 (d, J = 15.1 Hz, 1H), 3.07 - 2.94 (m, 1H), 1.71 - 1.60 (m, 2H) , 1.49 - 1.37 (m, 3H), 1.37 - 1.28 (m, 1H), 1.22 (d, J = 26.3 Hz, 6H), 0.84 (q, J = 12.5 Hz, 1H), 0.68 (dt, J = 46.7) , 13.5 Hz, 1H), 0.29 (s, 27H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 165.30, 140.35, 134.89, 128.35, 128.27, 127.10, 126.80, 124.93, 123.67, 121.63, 121.39, 111.07, 105.25, 70.93, 56.08, 51.20, 25.97 , 25.11, 25.04, 2.91.

Example 34: Synthesis of Procatalyst 36

To a solution of tetrakis-trimethylsilylmethyl hafnium (16.0 mg, _0.0302 mmol, 1.00 equiv) in C ₆ D ₆ (0.26 mL) in a nitrogen filled glovebox at 23° C. _was added guanidine (10.0 mg, 0.0302 mmol, 1.00 equiv) solution was added dropwise. After stirring for 90 minutes (300 rpm) an aliquot was removed and NMR showed complete conversion of the starting guanidine to the desired hafnium complex. The clear pale yellow solution was concentrated and concentrated by suspending in anhydrous deoxygenated pentane (3 mL), and this suspension/concentration process was repeated three more times to remove residual C ₆ D ₆ , and the obtained pale yellow amorphous foam was pentane (3 mL), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with pentane (3 x 3 mL), and the filtrate was concentrated to give hafnium complex (20.1 mg, 0.0261 mmol, 86) %) as a pale yellow amorphous foam. NMR showed the product.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.52 (dq, J = 8.3, 0.9 Hz, 1H), 7.48 - 7.45 (m, 1H), 7.18 - 7.13 (m, 1H), 7.05 (ddd, J ) = 8.1, 7.2, 1.0 Hz, 2H), 7.02 - 6.97 (m, 2H), 6.93 - 6.88 (m, 2H), 6.74 (dd, J = 3.3, 0.4 Hz, 1H), 6.36 (dd, J = 3.4) , 0.9 Hz, 1H), 4.31 (d, J = 15.0 Hz, 1H), 4.24 (d, J = 15.0 Hz, 1H), 3.17 (tt, J = 11.4, 4.0 Hz, 1H), 1.63 (m, 2H) ), 1.51 - 1.12 (m, 8H), 0.60 (s, 6H), 0.28 (s, 27H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 164.78, 140.04, 134.87, 128.42, 128.25, 127.49, 126.84, 124.89, 123.70, 121.70, 121.40, 111.11, 105.47, 77.15, 55.88, 50.85, 35.11. , 25.03, 3.27.

Example 35: Synthesis of Procatalyst 37

To a solution of ZrBn ₄ (23.9 mg, 0.0524 mmol, 1.00 equiv) in anhydrous deoxygenated C ₆ D ₆ (1.0 mL) at 23° C. in a nitrogen filled glovebox at 23° C. guanidine (20.0 mg, 0.0524 mmol) in C ₆ D ₆ (0.80 mL). , 1.00 equiv) solution was added dropwise. The now golden solution was stirred vigorously (1000 rpm) for 1 h, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated and suspended in anhydrous deoxygenated hexanes (3 mL) After concentration, this suspension/concentration process was repeated two more times to remove residual C ₆ D ₆ and PhMe, the obtained mixture was suspended in hexane (2 mL), PhMe (2 mL) was added, and the mixture was stirred for 2 Filtration through a 0.20 μm PTFE filter with vigorous stirring (1000 rpm) for min, concentrated the filtrate by washing with hexane/PhMe (3 x 3 mL, 1:1) to obtain a zirconium complex (36.1 mg, 0.0485 mmol, 92%) as a pale tan foam. NMR showed the product.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.79 - 7.75 (m, 2H), 7.24 (ddd, J = 8.3, 7.1, 1.3 Hz, 2H), 7.17 - 7.08 (m, 8H), 7.03 - 6.88 (m, 6H), 6.87 - 6.82 (m, 4H), 6.80 - 6.72 (m, 4H), 6.62 - 6.57 (m, 2H), 4.09 (s, 2H), 2.83 (tt, J = 11.6, 4.1 Hz) , 1H), 2.42 (s, 6H), 1.54 - 1.45 (m, 1H), 1.41 - 1.27 (m, 3H), 1.22 (d, J = 13.5 Hz, 2H), 1.02 (d, J = 13.2 Hz, 1H), 0.66 (qt, J = 13.0, 3.5 Hz, 1H), 0.41 (dddd, J = 16.8, 13.1, 8.3, 3.6 Hz, 2H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 165.27, 142.64, 139.77, 138.29, 130.53, 129.66, 128.30, 128.28, 128.15, 127.12, 126.57, 126.38, 124.09, 123.29, 123.17, 121.02, 120.44 , 57.47, 50.73, 34.69, 25.19, 24.93.

Example 36: Synthesis of Procatalyst 38

To a clear golden solution of HfBn ₄ (28.5 mg, 0.0524 mmol, 1.00 equiv) in anhydrous deoxygenated C ₆ D ₆ (1.0 mL) at 23° C. in a nitrogen filled glovebox with guanidine (20.0 mg) in C ₆ D ₆ (0.80 mL). , 0.0524 mmol, 1.00 equiv) solution was added dropwise. The now golden solution was stirred vigorously (1000 rpm) for 1 h, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated and suspended in anhydrous deoxygenated hexanes (3 mL) After concentration, this suspension/concentration process was repeated two more times to remove residual C ₆ D ₆ and PhMe, the obtained mixture was suspended in hexane (2 mL), PhMe (2 mL) was added, and the mixture was stirred for 2 Filtration through a 0.20 μm PTFE filter with vigorous stirring (1000 rpm) for min, concentrated the filtrate by washing with hexane/PhMe (3 x 3 mL, 1:1) to obtain hafnium complex (40.3 mg, 0.0484 mmol, 92%) as a pale tan foam. NMR showed the product.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.75 (ddd, J = 7.8, 1.3, 0.7 Hz, 2H), 7.23 - 7.17 (m, 8H), 7.00 (dt, J = 7.6, 1.2 Hz, 6H) ), 6.95 (dddd, J = 8.7, 3.5, 2.5, 1.2 Hz, 6H), 6.76 (d, J = 2.0 Hz, 1H), 6.75 - 6.73 (m, 2H), 6.54 - 6.46 (m, 3H), 4.07 (s, 2H), 2.99 (tt, J = 11.5, 4.2 Hz, 1H), 2.30 (s, 6H), 1.45 - 1.14 (m, 5H), 1.02 (d, J = 13.1 Hz, 1H), 0.68 (qt, J = 13.2, 3.7 Hz, 2H), 0.38 (tdd, J = 13.1, 9.4, 3.6 Hz, 2H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 164.21, 143.05, 139.33, 138.06, 128.99, 128.54, 128.22, 128.15, 128.03, 127.29, 126.65, 126.55, 123.45, 122.94, 121.22, 120.44, 110.78 , 50.48, 34.52, 25.05, 24.81.

Example 37: Synthesis of Procatalyst 41

To a solution of tetrakis _- trimethylsilylmethyl zirconium (11.5 mg, _0.0262 mmol, 1.00 equiv) in C ₆ D ₆ (0.23 mL) in a nitrogen filled glovebox at 23° C. , 0.0262 mmol, 1.00 equiv) solution was added dropwise. After stirring (300 rpm) for 90 min an aliquot was removed and NMR showed complete conversion of the starting guanidine to the desired zirconium complex. The clear pale yellow solution was concentrated and concentrated by suspending in anhydrous deoxygenated pentane (3 mL), and this suspension/concentration process was repeated three more times to remove residual C ₆ D ₆ , and the obtained pale yellow amorphous foam was pentane (3 mL), filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with pentane (3 x 3 mL), and the filtrate was concentrated to a zirconium complex (15.5 mg, 0.0211 mmol, 81) %) as a pale yellow amorphous foam. NMR showed the product.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.82 (d, J = 7.8 Hz, 2H), 7.53 (d, J = 8.2 Hz, 2H), 7.28 (t, J = 7.7 Hz, 2H), 7.13 - 7.08 (m, 2H), 6.86 - 6.82 (m, 2H), 6.80 - 6.76 (m, 3H), 4.21 (s, 2H), 3.10 - 3.01 (m, 1H), 1.75 - 1.68 (m, 2H) , 1.48 (qd, J = 11.8, 11.1, 6.9 Hz, 2H), 1.30 (s, 6H), 1.30 - 1.25 (m, 1H), 1.12 - 1.04 (m, 1H), 0.90 - 0.73 (m, 2H) , 0.57 - 0.45 (m, 2H), 0.34 (s, 27H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 164.76, 140.05, 138.27, 128.17, 128.06, 126.72, 126.65, 123.61, 121.30, 120.64, 110.60, 71.46, 56.20, 51.62, 35.89, 25.04, 24.96, 2.96.

Example 38: Synthesis of Procatalyst 43

To a solution of tetrakis-trimethylsilylmethyl zirconium (14.4 mg, _0.0328 mmol, 1.00 equiv) in C ₆ D ₆ (0.29 mL) in a nitrogen filled glovebox at 23° C. _was added guanidine (25.0 mg, 0.0655 mmol, 2.00 equiv) solution was added. The clear pale yellow solution was stirred (300 rpm) for 1 hour and then an aliquot was removed and NMR showed complete conversion to the desired complex. The solution was concentrated and concentrated by suspending in anhydrous deoxygenated pentane (3 mL), this suspension/concentration process was repeated three more times, and the obtained pale yellow foam was suspended in pentane (3 mL) to give a pale yellow mixture obtained by suspending in pentane (3 mL). Filtration through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washing with pentane (3 x 3 mL), and concentrating the filtrate gave the zirconium complex (29.4 mg, 0.0286 mmol, 87%) an off-white amorphous It was obtained as a foam. NMR showed the product.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.85 (d, J = 7.8 Hz, 4H), 7.68 (d, J = 8.2 Hz, 4H), 7.30 (t, J = 7.8 Hz, 4H), 7.12 (t, J = 5.2 Hz, 4H), 6.87 (d, J = 7.4 Hz, 4H), 6.80 (t, J = 7.5 Hz, 4H), 6.73 (t, J = 7.3 Hz, 2H), 4.57 (s) , 4H), 3.18 - 3.05 (m, 2H), 1.91 - 1.83 (m, 4H), 1.67 - 1.55 (m, 4H), 1.45 (s, 4H), 1.42 - 1.34 (m, 4H), 1.25 - 1.12 (m, 2H), 1.01 - 0.87 (m, 2H), 0.70 - 0.54 (m, 4H), 0.49 (s, 18H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 165.34, 140.20, 138.60, 128.14, 128.05, 126.41, 126.36, 123.56, 121.09, 120.57, 111.12, 68.13, 56.49, 51.91, 35.88, 24.96, 22.32, 13.87 .

Example 39: Synthesis of Procatalyst 44

To a solution of tetrakis-trimethylsilylmethyl hafnium (17.3 mg, 0.0328 mmol, 1.00 equiv) in C ₆ D ₆ (0.35 mL) in a nitrogen filled glovebox at 23° C. was added guanidine (25.0 mg) in C ₆ D ₆ (0.50 mL). , 0.0655 mmol, 2.00 equiv) solution was added. The clear pale yellow solution was stirred (300 rpm) for 1 hour and then an aliquot was removed and NMR showed complete conversion to the desired complex. The solution was concentrated and concentrated by suspending in anhydrous deoxygenated pentane (3 mL), this suspension/concentration process was repeated three more times, and the obtained pale yellow foam was suspended in pentane (3 mL) to give a pale yellow mixture obtained by suspending in pentane (3 mL). It was filtered through a 0.45 μm PTFE filter with vigorous stirring (1000 rpm) for 1 min, washed with pentane (3 x 3 mL), and the filtrate was concentrated to give the hafnium complex (33.4 mg, 0.0299 mmol, 91%) a pale yellow amorphous It was obtained as a foam. NMR showed the product.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.84 (d, J = 7.8 Hz, 4H), 7.67 (d, J = 8.2 Hz, 4H), 7.29 (t, J = 7.7 Hz, 4H), 7.12 (d, J = 7.2 Hz, 4H), 6.86 (d, J = 7.5 Hz, 4H), 6.79 (t, J = 7.5 Hz, 4H), 6.74 (d, J = 7.3 Hz, 2H), 4.62 (s) , 4H), 3.26 (t, J = 11.9 Hz, 2H), 1.92 - 1.82 (m, 4H), 1.68 - 1.58 (m, 4H), 1.42 - 1.33 (m, 4H), 1.25 - 1.12 (m, 2H) ), 1.01 - 0.87 (m, 2H), 0.85 (s, 4H), 0.67 - 0.54 (m, 4H), 0.51 (s, 18H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 164.40, 140.01, 138.67, 128.14, 126.46, 126.34, 123.58, 121.14, 120.57, 111.17, 68.15, 56.34, 51.70, 35.86, 24.96, 4.20.

Example 40: Synthesis of Procatalyst 49

To a clear colorless solution of Zr(CH ₂ SiMe ₃ ) ₄ (30.0 mg, 0.0682 mmol, 1.00 equiv) in anhydrous deoxygenated C ₆ D ₆ (1.0 mL) in a nitrogen-filled glovebox at 23° C., C ₆ D ₆ (0.80 mL) ) in guanidine (20.0 mg, 0.0682 mmol, 1.00 equiv) was added dropwise. The now golden solution was stirred vigorously (1000 rpm) for 1 h, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated and suspended in anhydrous deoxygenated pentane (3 mL) After concentration, this suspension/concentration process was repeated two more times to remove residual C ₆ D ₆ and Me ₄ Si, and the resulting mixture was suspended in pentane (3 mL) and filtered through a 0.20 μm PTFE filter, The filtrate was concentrated by washing with pentane (3 x 3 mL) to give the zirconium complex (35.2 mg, 0.0545 mmol, 80%) as a pale yellow foam. NMR showed the product.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.88 (dt, J = 7.8, 1.1 Hz, 2H), 7.58 (dt, J = 8.2, 0.9 Hz, 2H), 7.32 (ddd, J = 8.3, 5.8) , 1.2 Hz, 2H), 7.17 - 7.11 (m, 2H), 3.10 (q, J = 6.5 Hz, 2H), 1.32 (s, 6H), 0.90 (d, J = 6.5 Hz, 12H), 0.35 (s) , 27H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 163.21, 138.78, 126.76, 123.39, 121.18, 120.79, 109.98, 71.04, 48.01, 24.89, 2.99.

Example 41: Synthesis of Procatalyst 50

To a clear colorless solution of Hf(CH ₂ SiMe ₃ ) ₄ (36.0 mg, 0.0682 mmol, 1.00 equiv) in anhydrous deoxygenated C ₆ D ₆ (1.0 mL) in a nitrogen-filled glovebox at 23° C., C ₆ D ₆ (0.80 mL) ) in guanidine (20.0 mg, 0.0682 mmol, 1.00 equiv) was added dropwise. The now golden solution was stirred vigorously (1000 rpm) for 1 h, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated and suspended in anhydrous deoxygenated pentane (3 mL) After concentration, this suspension/concentration process was repeated two more times to remove residual C ₆ D ₆ and Me ₄ Si, and the resulting mixture was suspended in pentane (3 mL) and filtered through a 0.20 μm PTFE filter, The filtrate was concentrated by washing with pentane (3 x 3 mL) to give the hafnium complex (43.0 mg, 0.0587 mmol, 86%) as a pale yellow foam. NMR showed the product.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.88 (d, J = 7.7 Hz, 2H), 7.59 (d, J = 8.1 Hz, 2H), 7.37 - 7.30 (m, 2H), 7.14 (dd, J = 15.5, 7.8 Hz, 2H), 3.31 (p, J = 6.5 Hz, 2H), 0.90 (d, J = 6.4 Hz, 12H), 0.72 (s, 6H), 0.37 (s, 27H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 163.07, 138.81, 126.79, 123.49, 121.29, 120.81, 110.03, 77.17, 47.83, 24.78, 3.39.

Example 42: Synthesis of Procatalyst 55

To a clear golden solution of ZrBn ₄ (32.4 mg, 0.0711 mmol, 1.00 equiv) in anhydrous deoxygenated C ₆ D ₆ (1.0 mL) at 23° C. in a nitrogen-filled glovebox was guanidine (22.0 mg) in C ₆ D ₆ (0.88 mL). , 0.0711 mmol, 1.00 equiv) solution was added dropwise. The now golden solution was stirred vigorously (1000 rpm) for 1 h, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated and suspended in anhydrous deoxygenated hexanes (3 mL). This suspension/concentration process was repeated two more times to remove residual C ₆ D ₆ and PhMe, and the resulting mixture was suspended in hexane (2 mL) and PhMe (2 mL) was added, and the mixture was Filtered through a 0.20 μm PTFE filter with vigorous stirring (1000 rpm) for 2 min, concentrated the filtrate by washing with hexane/PhMe (3 x 3 mL, 1:1) to obtain a zirconium complex (47.1 mg, 0.0560 mmol) , 79%) as a golden orange foam. NMR showed the product.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.34 - 7.30 (m, 2H), 7.18 - 7.13 (m, 2H), 7.09 - 7.04 (m, 5H), 7.04 - 6.99 (m, 2H), 6.98 - 6.95 (m, 2H), 6.90 - 6.86 (m, 4H), 6.68 - 6.63 (m, 6H), 4.02 (s, 2H), 2.58 (q, J = 7.1 Hz, 4H), 2.31 (s, 6H) ), 2.11 (s, 6H), 0.39 (t, J = 7.1 Hz, 6H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 174.22, 146.19, 143.48, 141.85, 132.84, 129.39, 128.82, 128.43, 128.32, 128.17, 125.80, 124.10, 122.35, 72.59, 50.69, 39.98.48, 11.98.48

Example 43: Synthesis of procatalyst 57

To a clear golden solution of HfBn ₄ (22.0 mg, 0.0404 mmol, 1.00 equiv) in anhydrous deoxygenated C ₆ D ₆ (1.0 mL) at 23° C. in a nitrogen filled glovebox was guanidine (12.5 mg) in C ₆ D ₆ (0.48 mL). , 0.0404 mmol, 1.00 equiv) solution was added dropwise. The now golden solution was stirred vigorously (1000 rpm) for 1 h, an aliquot was removed, NMR showed complete conversion of the starting ligand, the solution was concentrated and suspended in anhydrous deoxygenated hexanes (3 mL) After concentration, this suspension/concentration process was repeated two more times to remove residual C ₆ D ₆ and PhMe, the obtained mixture was suspended in hexane (2 mL), PhMe (2 mL) was added, and the mixture was stirred for 2 Filtration through a 0.20 μm PTFE filter with vigorous stirring (1000 rpm) for min, concentrated the filtrate by washing with hexanes/PhMe (3 x 3 mL, 1:1) to obtain hafnium complex (29.0 mg, 0.0381 mmol, 94%) was obtained as a golden orange foam. NMR showed the product.

¹ H NMR (500 MHz, benzene- d ₆ ) δ 7.33 - 7.29 (m, 2H), 7.18 - 7.13 (m, 2H), 7.11 - 7.08 (m, 4H), 6.95 (dq, J = 7.3, 0.6 Hz) , 3H), 6.90 - 6.82 (m, 6H), 6.75 - 6.70 (m, 6H), 4.13 (s, 2H), 2.53 (q, J = 7.1 Hz, 4H), 2.30 (s, 6H), 1.91 ( s, 6H), 0.35 (t, J = 7.1 Hz, 6H). ¹³ C NMR (126 MHz, benzene- d ₆ ) δ 172.41, 145.18, 143.74, 141.53, 133.14, 128.94, 128.71, 128.45, 128.17, 126.47, 125.78, 124.54, 122.38, 80.43, 50.24, 39.89, 19.31, 12.00.

Example 44: Ligand 17 Synthesis

To a stirred (300 rpm) solution of Et ₂ NH (5 mL) was slowly added a solution of biscarbodiimide (98.0 mg, 0.2718 mmol, 1.00 equiv) in anhydrous deoxygenated THF (2 mL) dropwise over 1 min. After stirring at 27° C. for 72 hours, the pale yellow solution was concentrated, hexane (5 mL) was added to concentrate the mixture, and this process was repeated three more times to remove residual Et ₂ NH, and a viscous foam was formed with hexane (5 mL), filtered through a 0.45 μm ultrafine PTFE filter with vigorous stirring (1000 rpm), washed with hexane (3 x 3 mL), and concentrated to give bisguanidine (128.0 mg, 0.2526 mmol, 93%) dot. It was obtained as a white foam in nature. NMR showed the product.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.07 (d, J = 7.5 Hz, 4H), 6.88 (t, J = 7.4 Hz, 2H), 3.13 (q, J = 7.0 Hz, 10H), 2.59 - 2.47 (m, 4H), 2.21 (s, 12H), 1.06 (t, J = 7.1 Hz, 12H), 0.76 (p, J = 7.5 Hz, 4H), 0.55 (p, J = 7.7, 7.2 Hz, 2H). ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 153.15, 148.13, 129.14, 128.07, 121.44, 44.37, 42.61, 30.19, 23.61, 18.55, 12.85.

Example 45: Synthesis of Ligand 18

To a stirred (300 rpm) solution of i-Pr ₂ NH (5 mL) was slowly added dropwise a solution of biscarbodiimide (98.0 mg, 0.2718 mmol, 1.00 equiv) in anhydrous deoxygenated THF (2 mL). After stirring at 27°C for 24 hours, the now pale yellow solution was concentrated, hexane (5 mL) was added to concentrate the mixture, and this process was repeated three more times to remove residual i-Pr ₂ NH, and the viscous foam was Suspended in hexane (5 mL), filtered through a 0.45 μm ultrafine PTFE filter with vigorous stirring (1000 rpm), washed with hexane (3 x 3 mL), concentrated to bisguanidine (150.8 mg, 0.2679 mmol, 99%) ) as a clear colorless oil. NMR showed the product present as a mixture of isomers and rotomers.

The product exists as a mixture of isomers: (*) indicates minor isomers.

¹ H NMR (400 MHz, benzene- d ₆ ) δ 7.06 (dd, J = 7.5, 4.7 Hz, 4H), 6.90 - 6.78 (m, 2H), 3.69 (pd, J = 6.8, 2.1 Hz, 4H), 3.21 (t, J = 6.0 Hz, 2H) (2.84 (t, J = 6.8 Hz, 2H)*), (2.50 (q, J = 6.5 Hz, 4H)*) 2.47 - 2.40 (m, 4H), ( 2.27 (d, J = 0.8 Hz, 6H*) (2.26 (s, 6H)*) 2.24 (s, 12H), 1.20 (d, J = 6.8 Hz, 24H), (0.91 - 0.80 (m, 4H)* ) 0.75 (p, J = 7.5 Hz, 4H), 0.54 (p, J = 7.6, 7.0 Hz, 2H) ¹³ C NMR (101 MHz, benzene- d ₆ ) δ 152.22, 148.45, (132.07*) 128.77, 124.07, 120.84, 47.11 (46.09*), (44.03*) 44.01, (30.46*) 29.89 (29.76*), (23.83*) 23.77, 21.82, 18.87 (18.74*).

Example 46 - Polymerization Process

The catalytic activity (in terms of quench time, efficiency and polymer yield) and the obtained polymer properties were evaluated for procatalysts 1 to 74. The polymerization reaction was carried out in a parallel pressure reactor (PPR) and/or semi-batch reaction.

PPR polymerization experiments were carried out at both 120° C. and 150° C. using [HNMe(C ₁₈ H ₃₇ ) ₂ ][B(C ₆ F ₅ ) ₄ ] as an activator in an amount of 1.5 molar equivalents relative to the procatalyst, MMAO-3 (500 nmol at 120°C or 750 nmol at 150°C) was used as a scavenger. When the reactor temperature was 120° C., the ethylene pressure was 150 psi. When the reactor temperature was 150° C., the ethylene pressure was 213 psi. Reaction run times were 30 minutes, or 120° C. to 50 psi conversion or 150° C. to 75 psi conversion. The reaction was quenched with 10% CO.

The polymerization reaction in the semi-batch reactor was carried out in a 4-L semi-batch reactor without diethylzinc (DEZ) initially at 120 °C and 150 °C, and then at 150 °C, DEZ was subjected to three different loadings (0, 95 and 380). μmol). The activator was [HNMe(C ₁₈ H ₃₇ ) ₂ ][B(C ₆ F ₅ ) ₄ ] in an amount of 1.2 molar equivalents, and the scavenger was MMAO-3 (19.0 μmol). The run time for each polymerization experiment was 10 minutes.

To determine the chain transfer rate for the procatalyst, a semi-batch operation was performed using various amounts of the chain transfer agent Et ₂ Zn (amounts of 0, 95 and 380 μmol). All reactions used 1.2 equivalents of [HNMe(C ₁₈ H ₃₇ ) ₂ ][B(C ₆ F ₅ ) ₄ ] as an activator at 150°C. Batch operation was performed at 150° C. using 34 g of ethylene, 110 g of 1-octene and 1010 g of IsoparE under 163 psi pressure. The run time for each polymerization experiment was 10 minutes. The measured ethylene uptake as well as the Mw, PDI and comonomer incorporation of the corresponding polymers produced are presented in Table 3. Mn for each run was calculated using the appropriate Ca and Mn _values for using the Microsoft Excel Solver to minimize the squared deviation between the experimental molecular weight data and the fitted molecular weight data for all runs with a particular catalyst. It was calculated using Equation 3 with The calculated Ca values are presented in Table 4.

A high chain transfer constant of 1 or more for procatalysts 1, 15 and 55 at 150° C. indicates that these catalysts have high sensitivity to chain transfer agents and undergo rapid chain transfer with these chain transfer agents. For procatalysts 13, 37 and 56, only moderate sensitivity to chain shuttling agents (Ca ≥ 0.5) is observed. For procatalysts 1, 13, 15 and 56, a decrease in PDI or a persistent narrow PDI is observed as the amount of Et ₂ Zn(DEZ) is increased. This trend is evidence that procatalysts 1, 13, 15 and 56 are likely to undergo reversible chain transfer with chain shuttling agents, in contrast to irreversible chain transfer. This pattern was not observed in procatalysts 37, 38 or 55, and in these cases, an increase in PDI was observed as the amount of DEZ was increased, suggesting that the chain shuttling agent and irreversible chain transfer continue.

Claims (16)

A process for polymerizing polyolefins, said process comprising the step of contacting ethylene and optionally one or more (C ₃ -C ₁₂ )α-olefins in the presence of a catalyst system, said catalyst system comprising a metal according to formula (I) -contains a ligand structure,

In the above formula,
M is a metal selected from titanium, zirconium or hafnium, said metal having a formal oxidation state of +2, +3 or +4;
X is unsaturated (C ₂ -C ₂₀ )hydrocarbon, unsaturated (C ₂ -C ₅₀ )heterohydrocarbon, (C ₁ -C ₅₀ )hydrocarbyl, (C ₆ -C ₅₀ )aryl, (C ₆ -C ₅₀ )hetero is a monodentate or bidentate ligand independently selected from aryl, (C ₄ -C ₁₂ )diene, halogen, —OR ^C , —N(R ^N ) ₂ and —NCOR ^C ;
n is 1, 2 or 3;
m is 1 or 2;
m + n = 3 or 4;
each R ¹ is R ^1a or R ^1b ;
each R ⁴ is R ^4a or R ^4b ;
R ^1a , R ^1b , R ^4a and R ^4b are -H, (C ₁ -C ₄₀ )hydrocarbyl, (C ₁ -C ₄₀ )heterohydrocarbyl, (C ₁ -C ₄₀ )aryl, (C ₁ -C ₄₀ ) independently from heteroaryl, -P( ^RP ) ₂ , -N(R ^N ) ₂ , R ^C S(O)-, R ^C S(O) ₂ - or ( ^RC ) ₂ C=N- selected;
each A is independently —NR ¹ R ² ; wherein each R ² is R ^2a or R ^2b and each R ³ is R ^3a or R ^3b ; R ^2a , R ^2b , R ^3a and R ^3b are independently —H, (C ₁ -C ₄₀ )hydrocarbyl, (C ₁ -C ₄₀ )heterohydrocarbyl, (C ₁ -C ₄₀ )aryl or (C ₁ ) -C ₄₀ )heteroaryl;
only,
(1) when m is 2 and (2) when R ^2a , R ^2b , R ^3a and R ^3b are all methyl, then at least one of R ^1a , R ^1b , R ^4a and R ^4b is not 2-propyl;
when m is 1, each X is equal;
any of R ¹ and R ² , or R ² and R ³ , or R ³ and R ⁴ may optionally be joined to form a ring. 2. The method of claim 1, wherein m is 2, n is 2, and the metal-ligand complex has a structure according to formula (II),

In the above formula,
R ^1a , R ^1b , R ^4a , R ^4b , M and X are as defined in Formula (I) and A ¹ and A ² are independently A as defined in Formula (I). 3. The method of claim 2, wherein m is 2, n is 2, and R ^4a and R ^4b are covalently linked, whereby the metal-ligand complex consists of two covalently linked groups R ^4a and R ^4b . contains a divalent radical Q, wherein the metal-ligand complex has a structure according to formula (III),

In the above formula,
Q is (C ₂ -C ₁₂ )alkylene, (C ₂ -C ₁₂ )heteroalkylene, (C ₆ -C ₅₀ )arylene, (C ₄ -C ₅₀ )heteroarylene, (-CH ₂ Si( R ^C ) ₂ CH ₂ -), (-CH ₂ CH ₂ Si( ^RC ) ₂ CH ₂ CH ₂ -), (-CH ₂ Ge( ^RC ) ₂ CH ₂ -) or (-CH ₂ CH ₂ Ge (R ^C ) ₂ CH ₂ CH ₂ —);
R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b R ^4a , R ^4b , M and X are as defined in formula (I) and A ¹ and A ² are as defined in formula (II) As, method. 4. The method of any one of claims 1 to 3, wherein each X is the same. 5. The method according to any one of claims 1 to 4, wherein each X is benzyl, chloro, —CH ₂ SiMe ₃ or phenyl. 6. The method of any one of claims 1-5, wherein each R ¹ , R ^1a or R ^1b and each R ⁴ , R ^4a or R ^4b is independently (C ₁ -C ₂₀ )alkyl or (C ₁ ) -C ₂₀ )aryl, the method. 7. The method of any one of claims 1-6, wherein each R ¹ and each R ⁴ is independently benzyl, cyclohexyl, 2,6-dimethylphenyl, tert -butyl or ethyl. 4. The method of claim 3, wherein R ^1a and R ^1b are 2-propyl. 9. The method of any one of claims 1-8, wherein each A has one of the structures:

. 9. The method according to any one of claims 1 to 8, wherein R ^2a , R ^2b , R ^3a and R ^3b are (C ₁ -C ₁₂ )alkyl. 11. The method of claim 10, wherein R ^2a , R ^2b , R ^3a and R ^3b are methyl, ethyl, 1-propyl, 2-propyl, n-butyl, tert -butyl, 2-methylpropyl( iso -butyl), n- butyl, n-hexyl, cyclohexyl, n -octyl or tert -octyl. 6. The method of any one of claims 1 to 5, wherein R ^1a , R ^1b , R ^4a and R ^4b are 3,5-di- tert -butylphenyl; 2,4,6-trimethylphenyl; 2,6-dimethylphenyl; 2,4,6-triisopropylphenyl; 2,6-di- iso- propylphenyl; independently selected from benzyl, cyclohexyl or 2-propyl. The catalyst system according to claim 3 , wherein Q is selected from —(CH ₂ ) _x —, wherein x is 2 to 5. The catalyst system according to claim 3 , wherein Q is —(CH ₂ ) ₄ —. 15. The catalyst system of any one of claims 13-14, wherein the catalyst system further comprises a chain transfer agent. The catalyst system of claim 15 , wherein the chain transfer agent is diethylzinc.

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